[go: up one dir, main page]

CN101688099A - Adhesive composition, film-like adhesive, and connection structure of circuit member - Google Patents

Adhesive composition, film-like adhesive, and connection structure of circuit member Download PDF

Info

Publication number
CN101688099A
CN101688099A CN200880024283A CN200880024283A CN101688099A CN 101688099 A CN101688099 A CN 101688099A CN 200880024283 A CN200880024283 A CN 200880024283A CN 200880024283 A CN200880024283 A CN 200880024283A CN 101688099 A CN101688099 A CN 101688099A
Authority
CN
China
Prior art keywords
adhesive composition
circuit
adhesive
composition according
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200880024283A
Other languages
Chinese (zh)
Other versions
CN101688099B (en
Inventor
伊泽弘行
白坂敏明
加藤木茂树
工藤直
富泽惠子
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201210004210.9A priority Critical patent/CN102585709B/en
Priority to CN201210004719.3A priority patent/CN102559072B/en
Publication of CN101688099A publication Critical patent/CN101688099A/en
Application granted granted Critical
Publication of CN101688099B publication Critical patent/CN101688099B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29339—Silver [Ag] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29344—Gold [Au] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29347—Copper [Cu] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29355—Nickel [Ni] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/29393—Base material with a principal constituent of the material being a solid not provided for in groups H01L2224/293 - H01L2224/29391, e.g. allotropes of carbon, fullerene, graphite, carbon-nanotubes, diamond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83851—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester being an anisotropic conductive adhesive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00013—Fully indexed content
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01004—Beryllium [Be]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01013—Aluminum [Al]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0102—Calcium [Ca]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01023—Vanadium [V]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01032—Germanium [Ge]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01033—Arsenic [As]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01045—Rhodium [Rh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01049—Indium [In]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0105—Tin [Sn]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01074—Tungsten [W]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01077—Iridium [Ir]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01078—Platinum [Pt]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01084—Polonium [Po]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/0665—Epoxy resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/07802—Adhesive characteristics other than chemical not being an ohmic electrical conductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
    • H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/1026—Compound semiconductors
    • H01L2924/1032—III-V
    • H01L2924/10329—Gallium arsenide [GaAs]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/1026—Compound semiconductors
    • H01L2924/1032—III-V
    • H01L2924/10336—Aluminium gallium arsenide [AlGaAs]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/1026—Compound semiconductors
    • H01L2924/1032—III-V
    • H01L2924/10349—Aluminium gallium indium phosphide [AlGaInP]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19042—Component type being an inductor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0212—Resin particles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Adhesive Tapes (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Combinations Of Printed Boards (AREA)
  • Wire Bonding (AREA)

Abstract

The invention provides an adhesive composition, a film-like adhesive and a connection structure of a circuit member. The adhesive composition of the present invention is a composition containing organic fine particles containing at least one selected from the group consisting of an alkyl (meth) acrylate-butadiene-styrene copolymer or composite, an alkyl (meth) acrylate-silicone copolymer or composite, and a silicone- (meth) acrylic acid copolymer or composite.

Description

粘接剂组合物、膜状粘接剂和电路部件的连接结构 Adhesive composition, film adhesive, and connection structure of circuit components

技术领域 technical field

本发明涉及粘接剂组合物、膜状粘接剂和电路部件的连接结构The present invention relates to an adhesive composition, a film adhesive, and a connection structure of circuit components

背景技术 Background technique

出于使元件中的各种部件结合的目的，在半导体元件和液晶显示元件中，一直使用各种各样的粘接剂组合物。作为粘接剂组合物所要求的特性，首先要求满足粘接性，并且还要求满足耐热性、高温高湿状态下的可靠性等很多方面。Various adhesive compositions have been used in semiconductor elements and liquid crystal display elements for the purpose of bonding various components in the element. As the characteristics required of the adhesive composition, it is firstly required to satisfy adhesiveness, and also to satisfy many aspects such as heat resistance and reliability under high-temperature and high-humidity conditions.

此外，作为粘接所使用的被粘接物，以印刷电路板、聚酰亚胺等有机基材为首，可以使用由铜、铝等金属或ITO、SiN、SiO2等的具有各种各样的表面状态的基材。因此，粘接剂组合物需要针对各被粘接物进行分子设计。In addition, as the adherend used for bonding, organic substrates such as printed circuit boards and polyimide can be used, and metals such as copper and aluminum, or ITO, SiN, SiO2 , etc. can be used. The surface state of the substrate. Therefore, the adhesive composition needs to be molecularly designed for each adherend.

以往，作为半导体元件或液晶显示元件用的粘接剂组合物，一直应用的是使用了显示出高可靠性的环氧固化系或使用了自由基聚合性化合物的自由基固化系的热固性树脂(例如，参照专利文献1和2)。作为环氧固化系的粘接剂组合物的构成成分，通常使用环氧树脂、具有与环氧树脂反应性的酚树脂等固化剂、促进环氧树脂与固化剂反应的热潜在性催化剂。而另一方面，作为自由基固化系的粘接剂组合物的构成成分，正在使用丙烯酸酯衍生物或甲基丙烯酸酯衍生物等自由基聚合性化合物和作为自由基聚合引发剂的过氧化物。Conventionally, as an adhesive composition for a semiconductor element or a liquid crystal display element, an epoxy-curable thermosetting resin exhibiting high reliability or a radical-curable thermosetting resin using a radical polymerizable compound has been used ( For example, refer to Patent Documents 1 and 2). As constituent components of an epoxy-curable adhesive composition, generally, an epoxy resin, a curing agent such as a phenol resin reactive with the epoxy resin, and a thermolatent catalyst that promotes the reaction between the epoxy resin and the curing agent are used. On the other hand, radically polymerizable compounds such as acrylate derivatives and methacrylate derivatives and peroxides as radical polymerization initiators are being used as constituents of radical-curable adhesive compositions. .

然而，随着近来半导体元件的高集成化、液晶元件的高精细化，由于元件间和配线间间距狭小化，由于固化时的加热，因而有可能对周边部件产生不良影响。此外，为了降低成本，还需要提高生产量。相对于这些课题，要求在更低温度下且更短时间内进行固化，也就是说，要求在低温快速固化条件下的粘接。但是，用短时间进行固化时，已知由于固化收缩等，内部应力变大，粘接强度变低。另外，在低温下进行固化时，已知环氧树脂或丙烯酸酯衍生物或甲基丙烯酸酯衍生物不能充分进行反应，交联密度变得不足，可靠性降低。However, due to the recent high integration of semiconductor elements and high-definition liquid crystal elements, the spacing between elements and wiring has become narrower, and the heating during curing may have adverse effects on peripheral components. In addition, in order to reduce costs, it is also necessary to increase production volume. In order to overcome these problems, it is required to cure at a lower temperature and in a shorter time, that is, to require adhesion under low-temperature rapid curing conditions. However, when curing is performed in a short time, it is known that internal stress increases due to curing shrinkage and the like, and the adhesive strength decreases. In addition, when curing is performed at a low temperature, it is known that the reaction of the epoxy resin, acrylate derivatives, or methacrylate derivatives does not proceed sufficiently, and the crosslink density becomes insufficient, thereby reducing reliability.

另外，作为粘接强度的改善方法，提出了如下方法：通过使用具有醚键的自由基聚合性化合物，对粘接剂的固化物赋予可挠性，来改善粘接强度的方法(例如，参照专利文献3、4)；在粘接剂中分散由橡胶系弹性材料组成的应力吸收粒子，来改善粘接强度的方法(例如，参照专利文献5)。In addition, as a method of improving the adhesive strength, the method of improving the adhesive strength by imparting flexibility to the cured product of the adhesive by using a radically polymerizable compound having an ether bond (for example, see Patent Documents 3 and 4); a method of improving adhesive strength by dispersing stress-absorbing particles composed of a rubber-based elastic material in an adhesive (for example, refer to Patent Document 5).

专利文献1：日本特开平01-113480号公报Patent Document 1: Japanese Patent Application Laid-Open No. 01-113480

专利文献2：日本特开2002-203427号公报Patent Document 2: Japanese Unexamined Patent Publication No. 2002-203427

专利文献3：日本特许第3522634号公报Patent Document 3: Japanese Patent No. 3522634

专利文献4：日本特开2002-285128号公报Patent Document 4: Japanese Patent Laid-Open No. 2002-285128

专利文献5：日本特许第3477367号公报Patent Document 5: Japanese Patent No. 3477367

发明内容 Contents of the invention

发明要解决的问题The problem to be solved by the invention

但是，使用如上述专利文献3和4记载的具有醚键的自由基聚合性化合物的粘接剂，在低温下进行固化时，具有醚键的丙烯酸酯衍生物或甲基丙烯酸酯衍生物不能充分进行反应，存在交联密度变得不足这样的问题。进一步，即使是使用上述专利文献5记载的应力吸收粒子的粘接剂，由于应力吸收粒子的玻璃化温度(Tg)为80℃～120℃这样的高温，因此存在得不到充分的应力缓和效果这样的问题。因此，将这些粘接剂用于要求在高温高湿条件下(例如85℃/85％RH)长时间暴露后也稳定的性能的半导体元件或元件显示元件的粘接剂时，会产生在可靠性试验(高温高湿试验)后粘接力或连接电阻等特性恶化的问题。However, when the adhesives of radically polymerizable compounds having ether bonds described in Patent Documents 3 and 4 are cured at low temperatures, acrylate derivatives or methacrylate derivatives having ether bonds cannot sufficiently As the reaction progresses, there is a problem that the crosslink density becomes insufficient. Furthermore, even with the adhesive using the stress-absorbing particles described in the above-mentioned Patent Document 5, since the glass transition temperature (Tg) of the stress-absorbing particles is as high as 80°C to 120°C, there is a possibility that a sufficient stress relaxation effect cannot be obtained. such a problem. Therefore, when these adhesives are used as adhesives for semiconductor elements or element display elements that require stable performance even after long-term exposure to high temperature and high humidity conditions (such as 85°C/85%RH), there will be problems in reliability. After the test (high temperature and high humidity test), there is a problem that the characteristics such as adhesive force and connection resistance deteriorate.

本发明是鉴于上述现有技术中存在的课题而完成的，其目的在于提供一种显示优异的粘接强度，即使在可靠性试验(例如，85℃/85％RH放置)后也能够维持稳定的性能的粘接剂组合物、使用该粘接剂组合物的膜状粘接剂和电路部件的连接结构。The present invention has been made in view of the above-mentioned problems in the prior art, and an object thereof is to provide an adhesive that exhibits excellent adhesive strength and can be maintained stably even after a reliability test (for example, standing at 85°C/85%RH). The bonding structure of an adhesive composition having excellent performance, a film adhesive using the adhesive composition, and a circuit component.

解决问题的手段means of solving problems

为达到上述目的，本发明提供一种粘接剂组合物，其含有(a)包含从(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚物或复合物、(甲基)丙烯酸烷基酯-有机硅共聚物或复合物和有机硅-(甲基)丙烯酸共聚物或复合物组成的组中选出的至少一种物质的有机微粒。In order to achieve the above object, the present invention provides a kind of adhesive composition, it contains (a) comprises from (meth)acrylic acid alkyl ester-butadiene-styrene copolymer or compound, (meth)acrylic acid alkyl Organic microparticles of at least one substance selected from the group consisting of ester-silicon copolymers or complexes and silicone-(meth)acrylic acid copolymers or complexes.

该粘接剂组合物通过含有上述(a)有机微粒，不仅可以得到应力缓和性以及与树脂组合物的相溶性提高的效果，可以得到优异的粘接强度，而且可以充分降低连接电路部件彼此时的连接电阻，进一步在可靠性试验(例如，85℃/85％RH放置)后，也可以维持稳定性能。By containing the above-mentioned (a) organic fine particles, the adhesive composition can not only obtain the effect of improving stress relaxation and compatibility with the resin composition, but also obtain excellent adhesive strength, and can sufficiently reduce the time required for connecting circuit components. The connection resistance can also maintain stable performance after a reliability test (for example, 85°C/85%RH placement).

本发明的粘接剂组合物优选为含有(b)自由基聚合性化合物和(c)自由基聚合引发剂的组合物。该粘接剂组合物通过含有(b)自由基聚合性化合物和(c)自由基聚合引发剂，由于作为反应活性种的自由基富于反应性，因此能够在短时间固化。另外，不仅能够得到优异的粘接强度，而且在可靠性试验(高温高湿试验)后，也可以发挥优异的特性。The adhesive composition of the present invention is preferably a composition containing (b) a radical polymerizable compound and (c) a radical polymerization initiator. By containing (b) a radical polymerizable compound and (c) a radical polymerization initiator, the adhesive composition can be cured in a short time because radicals, which are reactive species, are highly reactive. In addition, not only excellent adhesive strength can be obtained, but also excellent characteristics can be exhibited after a reliability test (high temperature and high humidity test).

另外，本发明的粘接剂组合物优选为含有(d)环氧树脂和(e)潜在性固化剂的组合物。该粘接剂组合物通过含有(d)环氧树脂、(e)潜在性固化剂，不仅能够得到优异的粘接强度，而且在可靠性试验(高温高湿试验)后也可以发挥优异的特性。In addition, the adhesive composition of the present invention is preferably a composition containing (d) an epoxy resin and (e) a latent curing agent. By containing (d) epoxy resin and (e) latent curing agent, this adhesive composition can not only obtain excellent adhesive strength, but also exhibit excellent characteristics after reliability test (high temperature and high humidity test) .

在本发明的粘接剂组合物中，上述(a)有机微粒的Tg优选为-100～70℃。如果(a)有机微粒的Tg超过70℃时，由于不能充分的缓和粘接剂内部的应力，因此会有粘接强度下降的倾向。另外，如果(a)有机微粒的Tg不到-100℃，则得不到充分的凝集力，有降低粘接剂组合物物性的倾向。在上述专利文献5中所记载的应力吸收粒子的Tg为80～120℃这样的高温，应力缓和效果是不充分的。In the adhesive composition of the present invention, it is preferable that the Tg of the above-mentioned (a) organic fine particles is -100 to 70°C. (a) When the Tg of the organic fine particles exceeds 70°C, the stress inside the adhesive cannot be sufficiently relaxed, and thus the adhesive strength tends to decrease. In addition, if (a) the Tg of the organic fine particles is less than -100°C, sufficient cohesive force cannot be obtained, and the physical properties of the adhesive composition tend to decrease. The Tg of the stress-absorbing particles described in the above-mentioned Patent Document 5 is a high temperature of 80 to 120° C., and the stress relaxation effect is insufficient.

另外，在本发明的粘接剂组合物中，上述(a)有机微粒优选为包含具有三维交联结构的聚合物的粒子。由此，通过交联结构而发挥充足的凝集力，得到优异的粘接强度的同时，在可靠性试验(高温高湿试验)后也可以发挥优异的特性。In addition, in the adhesive composition of the present invention, the (a) organic fine particles are preferably particles containing a polymer having a three-dimensional crosslinked structure. Thereby, sufficient cohesive force can be exhibited by the crosslinked structure, excellent adhesive strength can be obtained, and excellent characteristics can also be exhibited after a reliability test (high-temperature high-humidity test).

本发明的粘接剂组合物中，上述(a)有机微粒优选为含有重均分子量为100万～300万的聚合物的粒子。由此，通过分子链的互相缠绕而发挥充足的凝集力，得到优异的粘接强度的同时，在可靠性试验(高温高湿试验)后也可以发挥优异的特性。In the adhesive composition of the present invention, the (a) organic fine particles are preferably particles containing a polymer having a weight average molecular weight of 1 million to 3 million. Thereby, sufficient cohesive force can be exhibited by mutual entanglement of molecular chains, excellent adhesive strength can be obtained, and excellent characteristics can also be exhibited after a reliability test (high temperature and high humidity test).

另外，在本发明的粘接剂组合物中，以粘接剂组合物的固体成分总量为基准，上述(a)有机微粒的含量优选为5～80质量％。(a)有机微粒的含量不到5质量％时，耐热性、凝集力可能不足，超过80质量％时，有流动性降低的危险。In addition, in the adhesive composition of the present invention, the content of the above-mentioned (a) organic fine particles is preferably 5 to 80% by mass based on the total solid content of the adhesive composition. (a) When the content of organic fine particles is less than 5% by mass, heat resistance and cohesive force may be insufficient, and when it exceeds 80% by mass, fluidity may decrease.

另外，在本发明的粘接剂组合物中，上述(a)有机微粒优选为具有核壳结构的粒子。由此，由于(a)有机微粒间相互作用被缓和，结构粘性(非牛顿粘度)变低，因此向树脂中的分散性提高，可以有效地得到(a)有机微粒的性能。In addition, in the adhesive composition of the present invention, the (a) organic fine particles are preferably particles having a core-shell structure. Thereby, since (a) the interaction between the organic fine particles is relaxed and the structural viscosity (non-Newtonian viscosity) becomes low, the dispersibility in the resin is improved, and the performance of (a) the organic fine particles can be effectively obtained.

本发明的粘接剂组合物，优选含有(f)分子内具有一个以上磷酸基的乙烯系化合物。由此，粘接剂组合物可以得到对于基材、特别是金属的优异的粘接强度。The adhesive composition of the present invention preferably contains (f) a vinyl compound having one or more phosphate groups in the molecule. Thereby, the adhesive composition can obtain excellent adhesive strength with respect to a base material, especially a metal.

本发明的粘接剂组合物，优选含有(g)热塑性树脂。粘接剂组合物通过含有上述(g)热塑性树脂，膜性提高，操作性变良好。The adhesive composition of the present invention preferably contains (g) a thermoplastic resin. When the adhesive composition contains the above-mentioned (g) thermoplastic resin, film properties are improved, and handleability becomes favorable.

另外，在本发明的粘接剂组合物中，上述(g)热塑性树脂优选为含有从苯氧树脂、聚酯树脂、聚氨酯树脂、聚酯型聚氨酯树脂、丁醛树脂、丙烯酸树脂和聚酰亚胺树脂组成的组中选出的至少一种的树脂。In addition, in the adhesive composition of the present invention, it is preferable that the above-mentioned (g) thermoplastic resin is selected from phenoxy resins, polyester resins, polyurethane resins, polyester polyurethane resins, butyral resins, acrylic resins, and polyimide resins. At least one resin selected from the group consisting of amine resins.

本发明的粘接剂组合物，优选含有(h)导电性粒子。The adhesive composition of the present invention preferably contains (h) conductive particles.

本发明还提供一种膜状粘接剂，其为将上述本发明的粘接剂组合物形成为膜状而成的。The present invention also provides a film-like adhesive obtained by forming the above-mentioned adhesive composition of the present invention into a film.

本发明进一步提供一种电路部件的连接结构，其具备相对设置的一对电路部件以及设置在所述一对电路部件之间的连接部件，该连接部件按照使所述一对电路部件所具有的电路电极彼此被电连接的方式将电路部件彼此粘接；其中，所述连接部件为由本发明的粘接剂组合物的固化物形成的部件。The present invention further provides a connection structure of circuit components, which includes a pair of circuit components disposed opposite to each other and a connection component provided between the pair of circuit components, and the connection component is configured according to the configuration of the pair of circuit components. The circuit components are bonded to each other in such a manner that the circuit electrodes are electrically connected to each other; wherein the connecting member is a member formed of a cured product of the adhesive composition of the present invention.

关于该电路部件的连接结构，由于其连接一对电路部件的连接部件由上述本发明的粘接剂组合物的固化物构成，因此不仅可以充分提高电路部件间的粘接强度，而且可以充分降低被电连接的电路电极间的连接电阻，进一步，即使在可靠性试验(例如，85℃/85％RH放置)后也可以发挥优异的特性。With regard to the connection structure of the circuit components, since the connection component connecting a pair of circuit components is composed of the cured product of the adhesive composition of the present invention, not only can the bonding strength between the circuit components be sufficiently improved, but also can be sufficiently reduced. The connection resistance between electrically connected circuit electrodes can exhibit excellent characteristics even after a reliability test (for example, 85° C./85% RH storage).

发明的效果The effect of the invention

根据本发明，可以提供一种显示优异的粘接强度，即使在可靠性试验(例如，85℃/85％RH放置)后，也可以维持稳定性能的粘接剂组合物、使用该粘接剂组合物的膜状粘接剂和电路部件的连接结构。According to the present invention, it is possible to provide an adhesive composition that exhibits excellent adhesive strength and can maintain stable performance even after a reliability test (for example, standing at 85°C/85%RH). The connection structure of the film adhesive of a composition and a circuit part.

附图说明 Description of drawings

图1为显示本发明的膜状粘接剂的一个实施方式的示意截面图。FIG. 1 is a schematic cross-sectional view showing one embodiment of the film adhesive of the present invention.

图2为显示本发明电路部件连接结构的一个实施方式的示意截面图。Fig. 2 is a schematic cross-sectional view showing one embodiment of the circuit component connection structure of the present invention.

图3的(a)～(c)为连接各电路部件的一系列工序图。(a)-(c) of FIG. 3 are a series of process diagrams of connecting each circuit component.

图4为显示半导体装置的一个实施方式的示意截面图。FIG. 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device.

符号说明Symbol Description

1    膜状粘接剂1 film adhesive

2    半导体装置2 semiconductor device

5    粘接剂成分5 Adhesive ingredients

7    导电性粒子7 Conductive particles

10   电路连接部件10 circuit connection parts

11   绝缘性物质11 Insulating substances

20   第1电路部件20 1st circuit components

21   电路基板(第1电路基板)21 Circuit board (1st circuit board)

21a  主面21a main face

22   电路电极(第1电路电极)22 Circuit electrodes (1st circuit electrodes)

30   第2电路部件30 2nd circuit component

31   电路基板(第2电路基板)31 Circuit board (second circuit board)

31a  主面31a main face

32   电路电极(第2电路电极)32 circuit electrode (second circuit electrode)

40   膜状电路连接材料40 Membrane circuit connection material

50   半导体元件50 semiconductor components

60   基板60 substrate

61   电路图案61 circuit patterns

70   密封材70 sealing material

80   半导体元件连接部件80 Semiconductor component connection parts

具体实施方式 Detailed ways

以下，根据需要参照附图，对本发明的优选实施方式进行详细说明。另外，在附图中，对同样或相当的部份赋予相同符号，并省略其重复说明。另外，本发明中，Tg是指通过动态粘弹性测定而得到的损耗因数(tan δ)的峰顶的温度。此外，本发明中，(甲基)丙烯酸是指丙烯酸或与其对应的甲基丙烯酸，(甲基)丙烯酸酯是指丙烯酸酯或与其对应的甲基丙烯酸酯，(甲基)丙烯酰基是指丙烯酰基或与其对应的甲基丙烯酰基。Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In addition, in the drawings, the same or corresponding parts are assigned the same reference numerals, and repeated description thereof will be omitted. In addition, in the present invention, Tg refers to the temperature of the peak top of the loss factor (tan δ) obtained by dynamic viscoelasticity measurement. In addition, in the present invention, (meth)acrylic acid refers to acrylic acid or its corresponding methacrylic acid, (meth)acrylate refers to acrylate or its corresponding methacrylate, (meth)acryloyl refers to acrylic Acyl or its corresponding methacryloyl.

本发明的粘接剂组合物含有(a)包含从(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚物或复合物、(甲基)丙烯酸烷基酯-有机硅共聚物或复合物和有机硅-(甲基)丙烯酸共聚物或复合物组成的组中选出的至少一种物质的有机微粒。另外，上述复合物是指各成分不共聚而进行复合化(混合)而得到的物质。The adhesive composition of the present invention contains (a) an alkyl (meth)acrylate-butadiene-styrene copolymer or compound, an alkyl (meth)acrylate-silicone copolymer or a compound organic particles of at least one substance selected from the group consisting of organic silicon-(meth)acrylic acid copolymers or composites. In addition, the above-mentioned composite refers to a substance in which each component is composited (mixed) without copolymerization.

这里，上述(甲基)丙烯酸烷基酯表示丙烯酸烷基酯、甲基丙烯酸烷基酯以及它们的混合物，(甲基)丙烯酸表示丙烯酸、甲基丙烯酸以及它们的混合物。Here, the above-mentioned alkyl (meth)acrylate means alkyl acrylate, alkyl methacrylate, and mixtures thereof, and (meth)acrylic acid means acrylic acid, methacrylic acid, and mixtures thereof.

另外，本发明的粘接剂组合物优选在含有上述(a)有机微粒的同时，含有(b)自由基聚合性化合物和(c)自由基聚合引发剂或者含有(d)环氧树脂和(e)潜在性固化剂。In addition, the adhesive composition of the present invention preferably contains (b) a radical polymerizable compound and (c) a radical polymerization initiator or (d) an epoxy resin and ( e) latent curing agent.

进一步，作为本发明的粘接剂组合物中含有的成分，优选可以举出(f)分子内具有一个以上磷酸基的乙烯系化合物、(g)热塑性树脂和(h)导电性粒子。以下，对各成分进行详细的说明。Furthermore, as a component contained in the adhesive composition of this invention, (f) the vinyl-type compound which has one or more phosphate groups in a molecule|numerator, (g) thermoplastic resin, and (h) electroconductive particle are mentioned preferably. Hereinafter, each component is demonstrated in detail.

本发明中，(a)有机微粒是包含从(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚物或复合物、(甲基)丙烯酸烷基酯-有机硅共聚物或复合物和有机硅-(甲基)丙烯酸共聚物或复合物组成的组中选出的至少一种物质的粒子。In the present invention, (a) organic microparticles are made from (meth)acrylic acid alkyl ester-butadiene-styrene copolymer or compound, (meth)acrylic acid alkyl ester-silicone copolymer or compound and Particles of at least one substance selected from the group consisting of silicone-(meth)acrylic acid copolymers or composites.

(a)有机微粒的Tg优选为-100～70℃。(a) Tg of the organic fine particles is preferably -100 to 70°C.

(a)有机微粒优选为包含具有三维交联结构的聚合物的粒子，和/或含有重均分子量为100万以上的聚合物的粒子。另外，构成(a)有机微粒的聚合物的重均分子量更优选为100万～300万。(a) The organic fine particles are preferably particles containing a polymer having a three-dimensional crosslinked structure, and/or particles containing a polymer with a weight average molecular weight of 1 million or more. Moreover, it is more preferable that the weight average molecular weight of the polymer which comprises organic microparticles|fine-particles of (a) is 1 million - 3 million.

另外，从对粘接剂组合物的分散性的观点出发，(a)有机微粒优选为在核材的表面形成有具有比该核材表面的玻璃化温度高的玻璃化温度的表面层的粒子，或在核材的表面使树脂接枝聚合而形成接枝层的粒子等核壳型的粒子。In addition, from the viewpoint of dispersibility to the adhesive composition, the (a) organic fine particles are preferably particles having a surface layer having a glass transition temperature higher than the glass transition temperature of the surface of the core material formed on the surface of the core material. , or a core-shell type particle such as a particle in which a resin is graft-polymerized on the surface of a core material to form a graft layer.

本发明的粘接剂组合物中，以粘接剂组合物的固体成分总量为基准，(a)有机微粒的含量优选为5～80质量％，更优选为10～70质量％。如果(a)有机微粒的含量不到5质量％，则耐热性、凝集力可能不足，超过80质量％时，则有流动性降低的危险。In the adhesive composition of the present invention, the content of (a) organic fine particles is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total solid content of the adhesive composition. If the content of (a) organic fine particles is less than 5% by mass, the heat resistance and cohesive force may be insufficient, and if it exceeds 80% by mass, the fluidity may decrease.

作为本发明中使用的(b)自由基聚合性化合物，没有特别的限定，可以使用公知的化合物。另外，(b)自由基聚合性化合物可以以单体、低聚物的任何一种形态来使用，也可以混合单体和低聚物而使用。The (b) radically polymerizable compound used in the present invention is not particularly limited, and known compounds can be used. In addition, the (b) radically polymerizable compound may be used in either form of a monomer or an oligomer, or may be used in admixture of a monomer and an oligomer.

作为(b)自由基聚合性化合物，具体可以举出环氧(甲基)丙烯酸酯低聚物、氨酯(甲基)丙烯酸酯低聚物、聚醚(甲基)丙烯酸酯低聚物、聚酯(甲基)丙烯酸酯低聚物等低聚物，三羟甲基丙烷三(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚亚烷基二醇二(甲基)丙烯酸酯、二环戊烯基(甲基)丙烯酸酯、二环戊烯氧基乙基(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、异氰尿酸改性2官能(甲基)丙烯酸酯，异氰尿酸改性3官能(甲基)丙烯酸酯，使(甲基)丙烯酸与双酚芴二缩水甘油醚的缩水甘油基加成所得的环氧(甲基)丙烯酸酯、将(甲基)丙烯酰氧基导入至使乙二醇或丙二醇与双酚芴二缩水甘油醚的缩水甘油基加成所得的化合物中而得到的化合物，以及下述通式(1)和(2)所表示的化合物等。这些化合物可以单独使用1种，或2种以上组合使用。Specific examples of (b) radically polymerizable compounds include epoxy (meth)acrylate oligomers, urethane (meth)acrylate oligomers, polyether (meth)acrylate oligomers, Oligomers such as polyester (meth)acrylate oligomers, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate base) acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, neopentyl glycol di(meth)acrylate, dipentaerythritol hexa(methyl) ) acrylate, isocyanuric acid modified 2-functional (meth)acrylate, isocyanuric acid-modified 3-functional (meth)acrylate, the glycidyl group of (meth)acrylic acid and bisphenol fluorene diglycidyl ether It is obtained by adding epoxy (meth)acrylate obtained by adding (meth)acryloyloxy group to a compound obtained by adding glycidyl group of ethylene glycol or propylene glycol to bisphenol fluorene diglycidyl ether compounds, and compounds represented by the following general formulas (1) and (2), etc. These compounds may be used alone or in combination of two or more.

[化1][chemical 1]

(式中，R1和R2分别独立地表示氢原子或甲基，k和1各自独立地表示1～8的整数。另外，式中，R1彼此之间和R2彼此之间可以各自相同也可以不同。)(In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and k and 1 each independently represent an integer of 1 to 8. In addition, in the formula, R 1 and R 2 may each independently same or different.)

[化2][Chem 2]

Figure G2008800242836D00072
Figure G2008800242836D00072

(式中，R3和R4各自独立地表示氢原子或甲基，m和n各自独立地表示0～8的整数。另外，式中，R3彼此之间和R4彼此之间可以各自相同也可以不同。)(In the formula, R 3 and R 4 each independently represent a hydrogen atom or a methyl group, and m and n each independently represent an integer from 0 to 8. In addition, in the formula, R 3 and R 4 may each independently same or different.)

在本发明的粘接剂组合物中，以粘接剂组合物的固体成分总量为基准，(b)自由基聚合性化合物的含量优选为15～70质量％，更优选为25～60质量％。该含量不到15质量％时，固化后的耐热性可能降低，超过60质量％时，则有成膜性降低的危险。In the adhesive composition of the present invention, the content of (b) the radically polymerizable compound is preferably 15 to 70% by mass, more preferably 25 to 60% by mass, based on the total solid content of the adhesive composition. %. When the content is less than 15% by mass, the heat resistance after curing may decrease, and when it exceeds 60% by mass, film-forming properties may decrease.

作为在本发明中使用的(c)自由基聚合引发剂，可以使用以往已知的过氧化物或偶氮化合物等公知化合物。从稳定性、反应性、相溶性的观点考虑，作为(c)自由基聚合引发剂，优选1分钟半衰期温度为90～175℃并且分子量为180～1,000的过氧化物。这里，“1分钟半衰期温度”是指半衰期为1分钟的温度，“半衰期”是指直到化合物的浓度减少至初期值的一半为止的时间。As the (c) radical polymerization initiator used in the present invention, known compounds such as conventionally known peroxides and azo compounds can be used. From the viewpoint of stability, reactivity, and compatibility, as (c) the radical polymerization initiator, a peroxide having a half-life temperature of 90 to 175° C. and a molecular weight of 180 to 1,000 in one minute is preferable. Here, the "1-minute half-life temperature" refers to the temperature at which the half-life is 1 minute, and the "half-life" refers to the time until the concentration of the compound decreases to half of the initial value.

作为(c)自由基聚合引发剂，具体可以列举1，1，3，3-四甲基丁基过氧化新癸酸酯、二(4-叔丁基环己基)过氧化二碳酸酯、二(2-乙基己基)过氧化二碳酸酯、枯基过氧化新癸酸酯、1，1，3，3-四甲基丁基过氧化新癸酸酯、二月桂酰基过氧化物、1-环己基-1-甲基乙基过氧化新癸酸酯、叔己基过氧化新癸酸酯、叔丁基过氧化新癸酸酯、叔丁基过氧化三甲基乙酸酯、1，1，3，3-四甲基丁基过氧化-2-乙基己酸酯、2，5-二甲基-2，5-二(2-乙基己酰基过氧化)己烷、叔己基过氧化-2-乙基己酸酯、叔丁基过氧化-2-乙基己酸酯、叔丁基过氧化新庚酸酯、叔戊基过氧化-2-乙基己酸酯、二叔丁基过氧化六氢对苯二甲酸酯、叔戊基过氧化-3，5，5-三甲基己酸酯、3-羟基-1，1-二甲基丁基过氧化新癸酸酯、1，1，3，3-四甲基丁基过氧化-2-乙基己酸酯、叔戊基过氧化新癸酸酯、叔戊基过氧化-2-乙基己酸酯、3-甲基苯甲酰基过氧化物、4-甲基苯甲酰基过氧化物、二(3-甲基苯甲酰基)过氧化物、二苯甲酰基过氧化物、二(4-甲基苯甲酰基)过氧化物、2，2’-偶氮二-2，4-二甲基戊腈、1，1’-偶氮二(1-乙酰氧基-1-苯基乙烷)、2，2’-偶氮二异丁腈、2，2’-偶氮二(2-甲基丁腈)、二甲基-2，2’-偶氮二异丁腈、4，4’-偶氮二(4-氰基戊酸)、1，1’-偶氮二(1-环己烷腈)、叔己基过氧化异丙基单碳酸酯、叔丁基过氧化马来酸、叔丁基过氧化-3，5，5-三甲基己酸酯、叔丁基过氧化月桂酸酯、2，5-二甲基-2，5-二(3-甲基苯甲酰基过氧化)己烷、叔丁基过氧化-2-乙基己基单碳酸酯、叔己基过氧化苯甲酸酯、2，5-二甲基-2，5-二(苯甲酰基过氧化)己烷、叔丁基过氧化苯甲酸酯、二丁基过氧化三甲基己二酸酯、叔戊基过氧化正辛酸酯、叔戊基过氧化异壬酸酯和叔戊基过氧化苯甲酸酯等。这些化合物可以单独使用1种，也可以2种以上组合使用。As the (c) radical polymerization initiator, specifically, 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, bis(2 -Ethylhexyl) peroxydicarbonate, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cycloyl peroxide Hexyl-1-methylethylperoxyneodecanoate, tert-hexylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperoxytrimethylacetate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, tert-hexylperoxide -2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneheptanoate, tert-amylperoxy-2-ethylhexanoate, di-tert-butyl Hexahydroterephthalate peroxide, tert-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate , 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxyneodecanoate, tert-amylperoxy-2-ethylhexanoate, 3 -Methylbenzoyl peroxide, 4-methylbenzoyl peroxide, bis(3-methylbenzoyl)peroxide, dibenzoyl peroxide, bis(4-methylbenzene formyl) peroxide, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2 , 2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'- Azobis(4-cyanovaleric acid), 1,1'-azobis(1-cyclohexanenitrile), tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butyl 3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-di(3-methylbenzoyl peroxide) Hexane, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-Butylperoxybenzoate, Dibutylperoxytrimethyladipate, tert-Amylperoxyn-octanoate, tert-Amylperoxy-isononanoate, and tert-Amylperoxybenzoate Etc. These compounds may be used alone or in combination of two or more.

另外，作为(c)自由基聚合引发剂，还可以使用由波长为150～750nm的光照射而产生自由基的化合物。作为这样的化合物，没有特别的限制，可以使用公知的化合物，例如，Photoinitiation，Photopolymerization，and Photocuring，J.-P.Fouassier，Hanser Publishers(1995年)，第17～35页中所记载的α-乙酰氨基酚衍生物或氧化膦衍生物，由于它们对光照射的敏感度高，因而更优选。这些化合物，可以单独使用1种，也可以和上述过氧化物或偶氮化合物混合来使用。Moreover, as (c) radical polymerization initiator, the compound which generate|occur|produces a radical by irradiation with the light of wavelength 150-750nm can also be used. As such compound, not particularly limited, can use known compound, for example, Photoinitiation, Photopolymerization, and Photocuring, J.-P.Fouassier, Hanser Publishers (1995), the α- Acetaminophen derivatives or phosphine oxide derivatives are more preferable because of their high sensitivity to light irradiation. These compounds may be used alone or in combination with the above-mentioned peroxide or azo compound.

在本发明的粘接剂组合物中，以粘接剂组合物的固体成分总量为基准，(c)自由基聚合引发剂的含量优选为0.1～50质量％，更优选为1～30质量％。该含量不到0.1质量％时，可能固化不足，超过50质量％时，会有放置稳定性降低的危险。In the adhesive composition of the present invention, the content of (c) the radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, based on the total solid content of the adhesive composition. %. When this content is less than 0.1 mass %, hardening may be insufficient, and when it exceeds 50 mass %, storage stability may fall.

作为在本发明中使用的(d)环氧树脂，例如可以举出：由表氯醇和双酚A或F、AD等衍生的双酚型环氧树脂，由表氯醇和苯酚线型酚醛树脂或甲酚线型酚醛树脂衍生的环氧线型酚醛树脂，具有含萘环的骨架的萘系环氧树脂，在缩水甘油胺、缩水甘油醚、联苯以及脂环式等的1个分子内具有2个以上的缩水甘油基的各种环氧化合物等。这些环氧化合物可以单独使用1种或2种以上组合使用。关于这些环氧树脂，为了防止电子迁移，优选使用杂质离子(Na+、Cl-等)或水解性氯等的浓度降低到300ppm以下的高纯度品。As the (d) epoxy resin used in the present invention, for example, bisphenol type epoxy resin derived from epichlorohydrin and bisphenol A or F, AD, etc., derived from epichlorohydrin and phenol novolak resin or Epoxy novolac resin derived from cresol novolak resin, naphthalene-based epoxy resin with a skeleton containing a naphthalene ring, has glycidylamine, glycidyl ether, biphenyl, and alicyclic type in one molecule Various epoxy compounds having two or more glycidyl groups, etc. These epoxy compounds can be used individually by 1 type or in combination of 2 or more types. For these epoxy resins, in order to prevent electron migration, it is preferable to use a high-purity product whose concentration of impurity ions (Na + , Cl -, etc.) or hydrolyzable chlorine is reduced to 300 ppm or less.

作为在本发明中使用的(e)潜在性固化剂，例如可以举出咪唑系固化剂、酰肼系固化剂、三氟化硼-胺络合物、锍盐、胺基酰亚胺、二氨基马来腈、三聚氰胺和其衍生物、聚胺的盐、双氰胺等，以及它们的改性物。这些物质可以单独使用1种或2种以上组合使用。这些物质是阴离子或阳离子聚合性的催化型固化剂，容易得到快速固化性，并且化学当量方面考虑得少也是可以的，因而优选。作为(e)潜在性固化剂，除了上述物质以外，还可以使用聚胺类、多硫醇、多酚、酸酐等加成聚合型固化剂。另外，也可以并用加成聚合型固化剂和催化型固化剂。Examples of the latent curing agent (e) used in the present invention include imidazole-based curing agents, hydrazide-based curing agents, boron trifluoride-amine complexes, sulfonium salts, aminoimides, bismuth Aminomaleonitrile, melamine and its derivatives, polyamine salts, dicyandiamide, etc., and their modified products. These substances may be used alone or in combination of two or more. These are anionically or cationicly polymerizable catalyst-type curing agents, which are easy to obtain rapid curing properties, and can be considered less in terms of chemical equivalents, so they are preferable. As the (e) latent curing agent, addition polymerization-type curing agents such as polyamines, polythiols, polyphenols, and acid anhydrides can be used in addition to the above-mentioned ones. In addition, an addition polymerization type curing agent and a catalytic type curing agent may be used in combination.

作为阴离子聚合型的催化型固化剂，优选为叔胺类或咪唑类。作为阳离子聚合型的催化型固化剂，由能量线照射而使环氧树脂固化时，优选为芳香族重氮盐、芳香族锍盐等感光性鎓盐。另外，除了能量线照射以外由加热进行活性化而使环氧树脂固化时，优选为脂肪族锍盐等。这些固化剂由于具有快速固化性这样的特征，因此是优选的。As the anionic polymerization type catalytic curing agent, tertiary amines or imidazoles are preferable. When curing an epoxy resin by irradiation of energy rays as a cationic polymerization-type catalytic curing agent, photosensitive onium salts such as aromatic diazonium salts and aromatic sulfonium salts are preferable. Moreover, when activation is performed by heating other than energy ray irradiation, and an epoxy resin is hardened, an aliphatic sulfonium salt etc. are preferable. These curing agents are preferred because of their rapid curing properties.

作为本发明中的(f)分子内具有1个以上的磷酸基的乙烯系化合物，例如可以举出下述通式(3)～(5)所表示的化合物。Examples of the vinyl compound having one or more phosphoric acid groups in the molecule of (f) in the present invention include compounds represented by the following general formulas (3) to (5).

[化3][Chem 3]

Figure G2008800242836D00101
Figure G2008800242836D00101

(式中，R5表示(甲基)丙烯酰基，R6表示氢原子或甲基，w和x各自独立地表示1～8的整数。另外，式中，R5彼此之间、R6彼此之间、w彼此之间和x彼此之间可以各自相同也可以不同。)(In the formula, R 5 represents a (meth)acryloyl group, R 6 represents a hydrogen atom or a methyl group, and w and x each independently represent an integer of 1 to 8. In addition, in the formula, between R 5 and R 6 between each other, w between each other and x between each other may be the same or different.)

[化4][chemical 4]

Figure G2008800242836D00102
Figure G2008800242836D00102

(式中，R7表示(甲基)丙烯酰基，y和z各自独立地表示1～8的整数。另外，式中，R7彼此之间、y彼此之间和x彼此之间可以各自相同也可以不同。)(In the formula, R 7 represents a (meth)acryloyl group, and y and z each independently represent an integer of 1 to 8. In addition, in the formula, R 7 each other, y each other and x each other can be the same can also be different.)

[化5][chemical 5]

Figure G2008800242836D00103
Figure G2008800242836D00103

(式中，R8表示(甲基)丙烯酰基，R9表示氢原子或甲基，a和b各自独立地表示1～8的整数。另外，式中，R9彼此之间和a彼此之间可以各自相同也可以不同。)(In the formula, R 8 represents a (meth)acryloyl group, R 9 represents a hydrogen atom or a methyl group, a and b each independently represent an integer of 1 to 8. In addition, in the formula, R 9 between each other and a between each other may be the same or different.)

作为(f)分子内具有一个以上的磷酸基的乙烯系化合物，具体可以举出酸式磷氧基乙基甲基丙烯酸酯、酸式磷氧基乙基丙烯酸酯、酸式磷氧基丙基甲基丙烯酸酯、酸式磷氧基聚氧乙二醇单甲基丙烯酸酯、酸式磷氧基聚氧丙二醇单甲基丙烯酸酯、2，2’-二(甲基)丙烯酰氧基二乙基磷酸酯、EO改性磷酸二甲基丙烯酸酯、磷酸改性环氧基丙烯酸酯、磷酸乙烯酯等。As (f) a vinyl compound having one or more phosphoric acid groups in the molecule, specific examples include acid phosphoroxy ethyl methacrylate, acid phosphoroxy ethyl acrylate, acid phosphoroxy propyl Methacrylate, Acid Phosphoroxypolyoxyethylene Glycol Monomethacrylate, Acid Phosphoroxypolyoxypropylene Glycol Monomethacrylate, 2,2'-Di(meth)acryloyloxydi Ethyl phosphate, EO modified phosphoric acid dimethacrylate, phosphoric acid modified epoxy acrylate, vinyl phosphate, etc.

在本发明的粘接剂组合物中，以粘接剂组合物的固体成分总量为基准，(f)分子内具有一个以上的磷酸基的乙烯系化合物的含量优选为0.1～15质量％，更优选为0.5～10质量％。该含量不到0.1质量％时，有难以得到高粘接强度的倾向，超过15质量％时，容易产生固化后粘接剂组合物的物性下降，可靠性可能会降低。In the adhesive composition of the present invention, based on the total solid content of the adhesive composition, the content of (f) vinyl compounds having one or more phosphate groups in the molecule is preferably 0.1 to 15% by mass, More preferably, it is 0.5-10 mass %. When the content is less than 0.1% by mass, it tends to be difficult to obtain high adhesive strength, and when it exceeds 15% by mass, the physical properties of the adhesive composition after curing tend to decrease, and reliability may decrease.

作为本发明中的(g)热塑性树脂，没有特别的限制，可以使用公知的树脂。作为这样的(g)热塑性树脂，可以使用苯氧树脂类、聚(甲基)丙烯酸酯类、聚酰亚胺类、聚酰胺类、聚氨酯类、聚酯类、聚酯型聚氨酯类、聚乙烯醇缩丁醛类等。这些中作为(g)热塑性树脂，优选使用苯氧树脂、聚酯树脂、聚氨酯树脂、聚酯型聚氨酯树脂、丁醛树脂、丙烯酸树脂、聚酰亚胺树脂。它们可以单独使用1种，或2种以上组合使用。The (g) thermoplastic resin in the present invention is not particularly limited, and known resins can be used. As such (g) thermoplastic resins, phenoxy resins, poly(meth)acrylates, polyimides, polyamides, polyurethanes, polyesters, polyester polyurethanes, polyethylene Alcohol butyral, etc. Among these, as (g) thermoplastic resin, phenoxy resin, polyester resin, polyurethane resin, polyester polyurethane resin, butyral resin, acrylic resin, and polyimide resin are preferably used. These can be used individually by 1 type, or in combination of 2 or more types.

这些热塑性树脂中也可以进一步含有硅氧烷键或氟取代基。组合使用这些热塑性树脂中的2种以上时，可以选择使用混合的树脂彼此完全相溶或者产生微相分离而成为白浊状态的2种以上树脂。另外，这些热塑性树脂分子量越大，越容易得到成膜性，可以将影响作为粘接剂组合物或膜状粘接剂的流动性的熔融粘度设定在更广的范围内。These thermoplastic resins may further contain a siloxane bond or a fluorine substituent. When two or more of these thermoplastic resins are used in combination, it is possible to select and use two or more resins in which the mixed resins are completely compatible with each other or undergo microphase separation and become cloudy. In addition, the larger the molecular weight of these thermoplastic resins, the easier it is to obtain film-forming properties, and the melt viscosity that affects the fluidity of the adhesive composition or film adhesive can be set within a wider range.

对于(g)热塑性树脂的分子量没有特别的限制，作为通常的重均分子量，优选为5,000～150,000，更优选为10,000～80,000。该值如果不到5,000，有成膜性下降的倾向，如果超过150,000，有和其它成分的相溶性变差的倾向。(g) The molecular weight of the thermoplastic resin is not particularly limited, but the usual weight average molecular weight is preferably 5,000 to 150,000, more preferably 10,000 to 80,000. If the value is less than 5,000, the film-forming property tends to decrease, and if it exceeds 150,000, the compatibility with other components tends to deteriorate.

在本发明的粘接剂组合物中，以粘接剂组合物的固体成分总量为基准，(g)热塑性树脂的含量优选为5～80质量％，更优选为15～70质量％。该含量不到5质量％时，有成膜性降低的倾向，如果超过80质量％，有粘接剂组合物流动性降低的倾向。In the adhesive composition of the present invention, the content of (g) thermoplastic resin is preferably 5 to 80 mass%, more preferably 15 to 70 mass%, based on the total solid content of the adhesive composition. When the content is less than 5% by mass, the film-forming property tends to decrease, and when it exceeds 80% by mass, the fluidity of the adhesive composition tends to decrease.

作为本发明的(h)导电性粒子，可以列举出例如Au、Ag、Ni、Cu、焊锡等金属粒子或碳粒子等。另外，(h)导电性粒子也可以是以非导电性的玻璃、陶瓷、塑料等为核体，在该核体上被覆上述金属、金属粒子、碳等而成的粒子。当(h)导电性粒子是以塑料为核体，在该核体上被覆上述金属、金属粒子或碳等而成的粒子、或为热熔融金属粒子时，由于具有加热加压变形性，因此在将电路部件彼此连接时，导电性粒子和电极的接触面积增加，可靠性提高，因而优选。As (h) electroconductive particle of this invention, metal particles, such as Au, Ag, Ni, Cu, solder, carbon particle, etc. are mentioned, for example. Moreover, (h) electroconductive particle may use non-conductive glass, ceramics, plastics, etc. as a nucleus, and the said metal, metal particle, carbon, etc. were coat|covered on this nucleus. When the (h) conductive particles are made of plastic as a nucleus, and the above-mentioned metal, metal particles, carbon, etc. are coated on the nucleus, or when they are hot-melt metal particles, since they have heat and pressure deformability, When connecting circuit members, since the contact area of electroconductive particle and an electrode increases and reliability improves, it is preferable.

此外，进一步用高分子树脂等被覆这些导电性粒子表面所得的微粒，可以抑制因导电性粒子的配合量增加而导致的粒子相互接触所引起的短路，可以提高电路电极间的绝缘性，因此，用高分子树脂等被覆导电性粒子表面所得的微粒可以单独使用，也可以和其它导电性粒子组合使用。In addition, the fine particles obtained by coating the surface of these conductive particles with a polymer resin or the like can suppress the short circuit caused by the mutual contact of the particles due to the increase in the compounding amount of the conductive particles, and can improve the insulation between the circuit electrodes. Therefore, Fine particles obtained by coating the surface of conductive particles with a polymer resin or the like may be used alone or in combination with other conductive particles.

(h)导电性粒子的平均粒径从得到良好的分散性和导电性的观点出发，优选为1～18μm。(h) The average particle diameter of electroconductive particle is preferable from a viewpoint of obtaining favorable dispersibility and electroconductivity, and it is 1-18 micrometers.

含有这样的(h)导电性粒子时，粘接剂组合物作为各向异性导电性粘接剂组合物可以很好地使用。When such (h) electroconductive particle is contained, an adhesive composition can be used suitably as an anisotropic electroconductive adhesive composition.

本发明的粘接剂组合物的(h)导电性粒子的含量没有特别的限制，以粘接剂组合物的固体成分总量为基准，优选为0.1～30体积％，更优选为0.1～10体积％。该含量不到0.1体积％时，有导电性恶化的倾向，如果超过30体积％时，有容易产生电路电极间短路的倾向。(h)导电性粒子的含量(体积％)是基于在23℃固化前的各成分的体积来确定的。各成分的体积，可以通过利用比重将质量换算为体积来求得。或者，也可以将不会使想要测定体积的成分溶解或溶胀而只是可以充分润湿该成分的适当溶剂(水、醇等)放入量筒等中，然后向其中投入测定对象，将增加的体积作为该成分的体积求出。The content of (h) conductive particles in the adhesive composition of the present invention is not particularly limited, but is preferably 0.1 to 30% by volume, more preferably 0.1 to 10%, based on the total solid content of the adhesive composition. volume%. When the content is less than 0.1% by volume, the conductivity tends to deteriorate, and when it exceeds 30% by volume, short circuits between circuit electrodes tend to easily occur. (h) Content (volume%) of electroconductive particle was determined based on the volume of each component before 23 degreeC hardening. The volume of each component can be obtained by converting mass into volume using specific gravity. Or, it is also possible to put an appropriate solvent (water, alcohol, etc.) that does not dissolve or swell the component whose volume is to be measured but can fully wet the component into a graduated cylinder, etc., and then put the measurement object into it, and the increased The volume was calculated|required as the volume of this component.

出于控制固化速度或赋予储藏稳定性的目的，在本发明的粘接剂组合物中还可以添加稳定剂。作为这样的稳定剂，没有特别的限制，可以使用公知的化合物，优选为苯醌或氢醌等醌衍生物、4-甲氧基苯酚或4-叔丁基邻苯二酚等酚衍生物、2，2，6，6-四甲基哌啶-1-氧基或4-羟基-2，2，6，6-四甲基哌啶-1-氧基等氨氧基(aminoxyl)衍生物、以及四甲基哌啶基甲基丙烯酸酯等受阻胺衍生物。A stabilizer may also be added to the adhesive composition of the present invention for the purpose of controlling the curing rate or imparting storage stability. Such a stabilizer is not particularly limited, and known compounds can be used, preferably quinone derivatives such as benzoquinone or hydroquinone, phenol derivatives such as 4-methoxyphenol or 4-tert-butylcatechol, 2, 2,6,6-tetramethylpiperidin-1-oxyl or 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl and other aminooxy (aminoxyl) derivatives, and Hindered amine derivatives such as tetramethylpiperidinyl methacrylate.

稳定剂的添加量，以粘接剂组合物的固体成分总量为基准，优选为0.01～30质量％，更优选为0.05～10质量％。该添加剂的量如果不到0.01质量％，则有不能充分得到添加效果的倾向，如果超过30质量％，则有与其它成分的相溶性降低的倾向。The added amount of the stabilizer is preferably 0.01 to 30% by mass, more preferably 0.05 to 10% by mass, based on the total solid content of the adhesive composition. If the amount of the additive is less than 0.01% by mass, the effect of addition tends not to be sufficiently obtained, and if it exceeds 30% by mass, the compatibility with other components tends to decrease.

本发明的粘接剂组合物中，还可以适宜地添加以烷氧基硅烷衍生物、硅氨烷衍生物为代表的偶联剂、密合提高剂、流平剂等粘接助剂。作为这样的粘接助剂，具体优选为以下述通式(6)所表示的化合物。这些粘接助剂，可以单独使用1种，或2种以上组合使用。Adhesive aids such as coupling agents typified by alkoxysilane derivatives and silazane derivatives, adhesion improving agents, and leveling agents may be added to the adhesive composition of the present invention as appropriate. As such an adhesion aid, specifically, a compound represented by the following general formula (6) is preferable. These adhesion aids can be used alone or in combination of two or more.

[化6][chemical 6]

Figure G2008800242836D00131
Figure G2008800242836D00131

(式中，R10、R11和R12各自独立地表示氢原子、碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为1～5的烷氧基羰基、或芳基，R13表示(甲基)丙烯酰基、乙烯基、异氰酸酯基、咪唑基、巯基、氨基、甲基氨基、二甲基氨基、苄基氨基、苯基氨基、环己基氨基、吗啉基、哌嗪基、脲基或缩水甘油基，c表示1～10的整数。)(In the formula, R 10 , R 11 and R 12 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms Alkoxycarbonyl, or aryl, R 13 represents (meth)acryloyl, vinyl, isocyanate, imidazolyl, mercapto, amino, methylamino, dimethylamino, benzylamino, phenylamino, ring Hexylamino, morpholino, piperazinyl, ureido or glycidyl, c represents an integer of 1 to 10.)

出于缓和应力和提高粘接性的目的，本发明的粘接剂组合物中还可以添加橡胶成分。作为橡胶成分，具体可以列举出聚异戊二烯、聚丁二烯、羧基末端聚丁二烯、羟基末端聚丁二烯、1，2-聚丁二烯、羧基末端1，2-聚丁二烯、羟基末端1，2-聚丁二烯、丙烯酸橡胶、苯乙烯-丁二烯橡胶、羟基末端苯乙烯-丁二烯橡胶、丙烯腈-丁二烯橡胶、在聚合物末端含有羧基、羟基、(甲基)丙烯酰基或吗啉基的丙烯腈-丁二烯橡胶、羧基化腈橡胶、羟基末端聚(氧丙烯)、烷氧基甲硅烷基末端聚(氧丙烯)、聚(氧四亚甲基)二醇、聚烯烃二醇以及聚-ε-己内酯。A rubber component may be added to the adhesive composition of the present invention for the purpose of relieving stress and improving adhesiveness. Specific examples of the rubber component include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, and carboxyl-terminated polybutadiene. Diene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, containing carboxyl groups at polymer ends, Hydroxy-, (meth)acryloyl- or morpholine-based acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly(oxypropylene), alkoxysilyl-terminated poly(oxypropylene), poly(oxypropylene) Tetramethylene) diol, polyolefin diol and poly-ε-caprolactone.

作为上述橡胶成分，从提高粘接性的观点考虑，优选在侧链或末端含有作为高极性基团的氰基或羧基的橡胶成分，从进一步提高流动性的观点考虑，更优选液状橡胶。作为橡胶成分的具体例子，可以列举出液状丙烯腈-丁二烯橡胶、在聚合物末端含有羧基、羟基、(甲基)丙烯酰基或吗啉基的液状丙烯腈-丁二烯橡胶、以及液状羧基化腈橡胶。在这些橡胶成分中优选作为极性基团的丙烯腈的含量为5～60质量％。这些化合物可以单独使用1种，也可以2种以上组合使用。The above-mentioned rubber component is preferably a rubber component containing a cyano group or a carboxyl group as a highly polar group in a side chain or terminal from the viewpoint of improving adhesiveness, and liquid rubber is more preferable from the viewpoint of further improving fluidity. Specific examples of the rubber component include liquid acrylonitrile-butadiene rubber, liquid acrylonitrile-butadiene rubber containing carboxyl, hydroxyl, (meth)acryloyl or morpholine groups at polymer terminals, and liquid acrylonitrile-butadiene rubber. Carboxylated nitrile rubber. The content of acrylonitrile as a polar group in these rubber components is preferably 5 to 60% by mass. These compounds may be used alone or in combination of two or more.

本发明的粘接剂组合物的使用状态没有特别的限制，例如可以使用将上述各成分溶解和/或分散在溶剂中而成的涂布液。作为溶剂没有特别的限制，例如可以举出甲苯、甲基乙基酮(MEK)、醋酸乙酯、醋酸异丙酯等。The use state of the adhesive composition of the present invention is not particularly limited, and for example, a coating solution obtained by dissolving and/or dispersing the above-mentioned components in a solvent can be used. The solvent is not particularly limited, and examples thereof include toluene, methyl ethyl ketone (MEK), ethyl acetate, isopropyl acetate, and the like.

另外，本发明的粘接剂组合物可以作为膜状粘接剂使用，所述膜状粘接剂是将含有上述各成分的组合物涂布在氟树脂膜、聚对苯二甲酸乙二醇酯膜、脱模纸等剥离性基材上，或者浸渍无纺布等基材并载放在剥离性基材上而形成的。In addition, the adhesive composition of the present invention can be used as a film-like adhesive obtained by coating a composition containing the above-mentioned components on a fluororesin film, polyethylene terephthalate, or polyethylene terephthalate. It is formed by impregnating a base material such as a non-woven fabric and placing it on a release base material such as an ester film or release paper.

图1是表示本发明的膜状粘接剂的一个实施方式的示意截面图。图1所示的膜状粘接剂1是将含上述各成分的粘接剂组合物形成为膜状而成的。根据该膜状粘接剂1，操作容易，可以容易地向被粘接体设置，能够容易地进行连接操作。另外，膜状粘接剂1也可以具有由2种以上的层形成的多层构成(未图示)。另外，膜状粘接剂1含有上述(h)导电性粒子(未图示)时，可以作为各向异性导电性膜而适宜地使用。FIG. 1 is a schematic cross-sectional view showing one embodiment of the film adhesive of the present invention. The film adhesive 1 shown in FIG. 1 is obtained by forming the adhesive composition containing the above-mentioned components into a film. According to this film adhesive 1, handling is easy, it can be easily installed on an adherend, and connection operation can be performed easily. In addition, the film adhesive 1 may have a multilayer structure (not shown) which consists of two or more types of layers. Moreover, when the film-form adhesive agent 1 contains said (h) electroconductive particle (not shown), it can be used suitably as an anisotropic electroconductive film.

本发明的粘接剂组合物和膜状粘接剂1通常可以并用加热和加压来使被粘接体彼此粘接。加热温度没有特别限制，优选为100～250℃的温度。压力只要是在不会对被粘接体产生损伤的范围，就不受特别限制，通常优选为0.1～10MPa。该加热和加压，优选在0.5秒～120秒间的范围进行。本发明的粘接剂组合物和膜状粘接剂1能够在低温且短时间内固化，因此，例如在140～200℃、3MPa的条件下，即使以10秒的短时间加热和加压，也可以使被粘接体彼此被充分粘接。The adhesive composition of the present invention and the film-like adhesive 1 can usually be used in combination to adhere adherends to each other by heating and pressurizing. The heating temperature is not particularly limited, but is preferably a temperature of 100 to 250°C. The pressure is not particularly limited as long as it is within a range that does not damage the adherend, but usually it is preferably 0.1 to 10 MPa. The heating and pressurization are preferably performed within a range of 0.5 seconds to 120 seconds. The adhesive composition and film adhesive 1 of the present invention can be cured at a low temperature and in a short time. Therefore, for example, under the conditions of 140 to 200° C. and 3 MPa, heating and pressurizing in a short time of 10 seconds, It is also possible to sufficiently bond the adherends to each other.

另外，本发明的粘接剂组合物和膜状粘接剂1可以作为热膨胀系数不同的多种被粘接物的粘接剂而使用。具体来说，可以作为以各向异性导电性粘接剂、银糊、银膜等为代表的电路连接材料，以CSP用弹性体、CSP用底部填充材料、LOC带等为代表的半导体元件粘接材料。In addition, the adhesive composition and film adhesive 1 of the present invention can be used as an adhesive for various adherends having different thermal expansion coefficients. Specifically, it can be used as circuit connection materials represented by anisotropic conductive adhesives, silver pastes, silver films, etc., semiconductor element adhesives represented by CSP elastomers, CSP underfill materials, LOC tapes, etc. connect material.

以下，对于使用本发明的膜状粘接剂作为各向异性导电性膜，来连接在电路基板的主面上形成有电路电极的电路部件彼此时的一个例子进行说明。即，可以将各向异性导电性膜配置在电路基板上的相对的电路电极间，通过加热加压，进行相对的电路电极间的电连接和电路基板间的粘接，来连接电路部件彼此。在这里，作为形成电路电极的电路基板，可以使用由半导体、玻璃、陶瓷等无机物形成的基板，由聚酰亚胺、聚碳酸酯等有机物形成的基板，组合玻璃/环氧树脂等无机物和有机物而成的基板等。另外，在作为像这样的电路连接材料的用途中使用本发明的膜状粘接剂时，优选在这些中含有导电性粒子。另外，可以使用本发明的粘接剂组合物替代膜状粘接剂，将其直接涂布在电路基板上。Hereinafter, an example of connecting circuit components having circuit electrodes formed on the main surface of a circuit board using the film adhesive of the present invention as an anisotropic conductive film will be described. That is, the anisotropic conductive film can be disposed between opposing circuit electrodes on a circuit board, and the electrical connection between the opposing circuit electrodes and the bonding between the circuit boards can be performed by heating and pressing, thereby connecting circuit components to each other. Here, as the circuit board on which the circuit electrodes are formed, substrates made of inorganic materials such as semiconductors, glass, and ceramics, substrates made of organic materials such as polyimide and polycarbonate, and inorganic materials such as glass/epoxy resins combined can be used. and substrates made of organic matter. Moreover, when using the film-form adhesive agent of this invention for the use as such a circuit connection material, it is preferable to contain electroconductive particle in these. In addition, the adhesive composition of the present invention may be used instead of a film-like adhesive and directly coated on a circuit board.

图2为显示本发明电路连接结构体(电路部件的连接结构)的一个实施方式的示意截面图。如图2所示，本实施方式的电路部件的连接结构具有相互相对的第一电路部件20和第二电路部件30，在第一电路部件20和第二电路部件30之间设置有连接它们的电路连接部件10。FIG. 2 is a schematic cross-sectional view showing one embodiment of the circuit connection structure (connection structure of circuit components) of the present invention. As shown in FIG. 2 , the connection structure of the circuit components of this embodiment has a first circuit component 20 and a second circuit component 30 facing each other, and a connection between the first circuit component 20 and the second circuit component 30 is provided. Circuit connection part 10.

第一电路部件20具有电路基板(第一电路基板)21和电路基板21的主面21a上所形成的电路电极(第一电路电极)22。另外，在电路基板21的主面21a上根据情况还可以形成绝缘层(未图示)。The first circuit component 20 has a circuit board (first circuit board) 21 and a circuit electrode (first circuit electrode) 22 formed on the main surface 21 a of the circuit board 21 . In addition, an insulating layer (not shown) may be formed on the main surface 21 a of the circuit board 21 as the case may be.

另一方面，第二电路部件30具有电路基板(第二电路基板)31和电路基板31的主面31a上所形成的电路电极(第二电路电极)32。另外，在电路基板31的主面31a上根据情况还可以形成绝缘层(未图示)。On the other hand, the second circuit member 30 has a circuit board (second circuit board) 31 and a circuit electrode (second circuit electrode) 32 formed on the main surface 31 a of the circuit board 31 . In addition, an insulating layer (not shown) may be formed on the main surface 31 a of the circuit board 31 as the case may be.

作为第一和第二电路部件20、30，只要是形成有需要电连接的电极的部件，就没有特别的限制。具体可以举出以在液晶显示器中使用的以ITO等形成电极的玻璃或塑料基板、印刷线路板、陶瓷线路板、挠性线路板、半导体硅芯片等，这些可以根据需要而组合使用。像这样在本实施方式中，以印刷线路板或由聚酰亚胺等有机材料形成的材质为首，可以使用铜、铝等金属或像ITO(indium tin oxide)、氮化硅(SiNx)、二氧化硅(SiO2)等无机材质这样的具有各种各样表面状态的电路部件。There are no particular limitations on the first and second circuit components 20 and 30 as long as electrodes to be electrically connected are formed therein. Specific examples include glass or plastic substrates, printed wiring boards, ceramic wiring boards, flexible wiring boards, semiconductor silicon chips, etc., which are used in liquid crystal displays with electrodes formed of ITO or the like, and these can be used in combination as necessary. In this way, in this embodiment, materials such as printed circuit boards or organic materials such as polyimide, metals such as copper and aluminum, or materials such as ITO (indium tin oxide), silicon nitride (SiNx), and bismuth can be used. Circuit components with various surface states such as inorganic materials such as silicon oxide (SiO 2 ).

电路连接部件10由本发明的粘接剂组合物或膜状粘接剂的固化物形成。该电路连接部件10含有绝缘性物质11和导电性粒子7。导电性粒子7不仅配置在相对的电路电极22和电路电极32之间，还设置在主面21a彼此之间、31a彼此之间。在电路部件的连接结构中，电路电极22、32通过导电性粒子7而被电连接。即，导电性粒子7与电路电极22、32的双方直接接触。The circuit connection member 10 is formed from the cured product of the adhesive composition or film-like adhesive of the present invention. This circuit connection member 10 contains an insulating substance 11 and conductive particles 7 . Electroconductive particle 7 is arrange|positioned not only between the circuit electrode 22 and the circuit electrode 32 which oppose, but also between main surfaces 21a and 31a. In the connection structure of the circuit components, the circuit electrodes 22 and 32 are electrically connected through the conductive particles 7 . That is, electroconductive particle 7 is in direct contact with both circuit electrodes 22 and 32 .

在这里，导电性粒子7是前面所说明的(h)导电性粒子，绝缘性物质11是构成本发明的粘接剂组合物和膜状粘接剂的绝缘性各成分的固化物。Here, the electroconductive particle 7 is (h) electroconductive particle demonstrated above, and the insulating substance 11 is hardened|cured material of each insulating component which comprises the adhesive composition of this invention and a film adhesive.

在该电路部件的连接结构中，如上所述，通过导电性粒子7电连接相对的电路电极22和电路电极32。因此，电路电极22、32间的连接电阻被充分降低。所以可以顺利地进行电路电极22、32间的电流流动，充分发挥电路所具有的功能。另外，电路连接部件10不含导电性粒子7时，电路电极22和电路电极32通过直接接触而被电连接。In the connection structure of this circuit member, as mentioned above, the opposing circuit electrode 22 and the circuit electrode 32 are electrically connected via the electroconductive particle 7. As shown in FIG. Therefore, the connection resistance between the circuit electrodes 22 and 32 is sufficiently reduced. Therefore, the current flow between the circuit electrodes 22 and 32 can be smoothly performed, and the functions of the circuit can be fully exhibited. Moreover, when the circuit connection member 10 does not contain the electroconductive particle 7, the circuit electrode 22 and the circuit electrode 32 are electrically connected by direct contact.

由于电路连接部件10由本发明的粘接剂组合物或膜状粘接剂的固化物构成，因此电路连接部件10对电路部件20或30的粘接强度变得充分高，在可靠性试验(高温高湿试验)后也可以维持稳定的性能(粘接强度或连接电阻)。Since the circuit connecting member 10 is composed of the adhesive composition of the present invention or a cured product of the film adhesive, the bonding strength of the circuit connecting member 10 to the circuit member 20 or 30 becomes sufficiently high, and the reliability test (high temperature High humidity test) can maintain stable performance (adhesive strength or connection resistance).

然后，说明有关上述电路部件的连接结构制造方法的一个例子。首先，准备上述的第一电路部件20和膜状粘接剂(膜状电路连接材料)40(参照图3(a))。膜状电路连接材料40是将本发明的粘接剂组合物(电路连接材料)成形为膜状而成的材料，含有导电性粒子7和粘接剂成分5。另外，电路连接材料不含导电性粒子7时，该电路连接材料可以作为绝缘性粘接剂用于各向异性导电性粘接，特别是有时被称为NCP(Non Conductive Paste，非导电胶)。电路连接材料包含导电性粒子7时，该电路连接材料可称为ACP(AnisotropicConductive Paste，各向异性导电胶)。Next, an example of a method for manufacturing a connection structure of the above-mentioned circuit components will be described. First, the first circuit member 20 and the film adhesive (film circuit connecting material) 40 described above are prepared (see FIG. 3( a )). The film-form circuit connection material 40 is what molded the adhesive composition (circuit connection material) of this invention into a film shape, and contains the electroconductive particle 7 and the adhesive agent component 5. In addition, when the circuit connection material does not contain conductive particles 7, the circuit connection material can be used as an insulating adhesive for anisotropic conductive bonding, and it is sometimes called NCP (Non Conductive Paste, non-conductive paste) in particular. . When the circuit connection material contains conductive particles 7 , the circuit connection material may be called ACP (Anisotropic Conductive Paste, Anisotropic Conductive Paste).

膜状电路连接材料40的厚度优选为10～50μm。膜状电路连接材料40的厚度不到10μm时，会有电路电极22、32之间电路连接材料填充不足的倾向。另一方面，超出50μm时，会变得不能彻底排出电路电极22、32间的粘接剂组合物，有很难确保电路电极22、32之间的导通的倾向。It is preferable that the thickness of the film-form circuit connection material 40 is 10-50 micrometers. When the thickness of the film-form circuit connection material 40 is less than 10 micrometers, there exists a tendency for the filling of the circuit connection material between the circuit electrodes 22 and 32 to be insufficient. On the other hand, if it exceeds 50 μm, the adhesive composition between the circuit electrodes 22 and 32 cannot be completely discharged, and it tends to be difficult to secure the conduction between the circuit electrodes 22 and 32 .

接着，将膜状电路连接材料40放在形成有第一电路部件20的电路电极22的面上。膜状电路连接材料40附着在支撑体(未图示)上时，按照使膜状电路连接材料40侧的一面以朝向第一电路部件20的方式放置在第一电路部件20上。这时，膜状电路连接材料40为膜状，操作容易。因此，膜状电路连接材料40容易介于第一电路部件20和第二电路部件30之间，可以容易地进行第一电路部件20和第二电路部件30的连接操作。Next, the film-like circuit connecting material 40 is placed on the surface on which the circuit electrodes 22 of the first circuit member 20 are formed. When the film-like circuit-connecting material 40 is attached to a support (not shown), it is placed on the first circuit member 20 so that the side of the film-like circuit-connecting material 40 faces the first circuit member 20 . In this case, the film-form circuit-connecting material 40 is film-form and easy to handle. Therefore, the film-like circuit connecting material 40 is easily interposed between the first circuit member 20 and the second circuit member 30, and the connection operation of the first circuit member 20 and the second circuit member 30 can be easily performed.

然后，沿着图3(a)的箭头A和B方向对膜状电路连接材料40加压，使膜状电路连接材料40临时连接在第一电路部件20上(参照图3(b))。这时，也可以一边加热一边加压。加热温度为膜状电路连接材料40中的粘接剂组合物不固化的温度，即，比自由基聚合引发剂产生自由基的温度低的温度。Then, the film-like circuit-connecting material 40 is pressurized in the directions of arrows A and B in FIG. 3( a ), and the film-like circuit-connecting material 40 is temporarily connected to the first circuit member 20 (see FIG. 3( b )). At this time, pressure may be applied while heating. The heating temperature is a temperature at which the adhesive composition in the film-like circuit connecting material 40 is not cured, that is, a temperature lower than the temperature at which the radical polymerization initiator generates radicals.

接着，如图3(c)所示，按照使第二电路电极向着第一电路部件20的方式，将第二电路部件30放在膜状电路连接材料40上。另外，膜状电路连接材料40附着在支撑体(未图示)上时，剥离支撑体后将第二电路部件30放在膜状电路连接材料40上。Next, as shown in FIG. 3( c ), the second circuit member 30 is placed on the film-like circuit connecting material 40 so that the second circuit electrode faces the first circuit member 20 . Moreover, when the film-form circuit connection material 40 adheres to the support body (not shown), after peeling off a support body, the 2nd circuit member 30 is put on the film-form circuit connection material 40.

之后，加热膜状电路连接材料40的同时，沿着图3(c)的箭头A和B方向隔着第一和第二电路部件20、30进行加压。这时的加热温度为自由基聚合引发剂能够产生自由基的温度。由此，自由基聚合引发剂产生自由基，开始自由基聚合性化合物的聚合。这样膜状电路连接材料40被固化处理而进行正式的连接，得到如图2所示的电路部件的连接结构。Thereafter, while heating the film-form circuit-connecting material 40, pressure is applied across the first and second circuit members 20, 30 along the directions of arrows A and B in FIG. 3(c). The heating temperature at this time is the temperature at which the radical polymerization initiator can generate radicals. Thereby, the radical polymerization initiator generates radicals, and the polymerization of the radical polymerizable compound starts. In this way, the film-like circuit-connecting material 40 is cured to perform actual connection, and a connection structure of circuit components as shown in FIG. 2 is obtained.

在这里，连接条件如前所述，加热温度优选为100～250℃，压力为0.1～10MPa，连接时间为0.5秒～120秒。这些条件可根据使用的用途、粘接剂组合物、电路部件来适当选择，根据需要，也可进行后固化。Here, the connection conditions are as described above, and the heating temperature is preferably 100-250° C., the pressure is 0.1-10 MPa, and the connection time is 0.5 seconds to 120 seconds. These conditions can be appropriately selected according to the purpose of use, the adhesive composition, and the circuit component, and post-curing may be performed as necessary.

通过如上所述制造电路部件的连接结构，在得到的电路部件的连接结构中，能够使导电性粒子7与相对的电路电极22、32二者接触，可以充分减少电路电极22、32之间的连接电阻。By manufacturing the connection structure of the circuit components as described above, in the connection structure of the obtained circuit components, the conductive particles 7 can be brought into contact with both the opposing circuit electrodes 22, 32, and the friction between the circuit electrodes 22, 32 can be sufficiently reduced. Connect the resistor.

另外，通过加热膜状电路连接材料40，在使电路电极22和电路电极32之间的距离非常小的状态下，粘接剂成分5固化而成为绝缘性物质11，第一电路部件20和第二电路部件30通过电路连接部件10而被牢固地连接。即，在得到的电路部件的连接结构中，由于电路连接部件10由本发明的膜状粘接剂组成的电路连接材料的固化物构成，所以电路连接部10对电路部件20和30的粘接强度变得非常高，而且可以充分减少电连接的电路电极间的连接电阻。In addition, by heating the film-like circuit connecting material 40, in the state where the distance between the circuit electrode 22 and the circuit electrode 32 is very small, the adhesive component 5 is cured to become the insulating substance 11, and the first circuit member 20 and the second circuit member 20 are connected to each other. The two circuit components 30 are firmly connected by the circuit connection component 10 . That is, in the connection structure of the obtained circuit components, since the circuit connection component 10 is composed of a cured product of the circuit connection material composed of the film adhesive of the present invention, the bonding strength of the circuit connection part 10 to the circuit components 20 and 30 becomes very high, and can sufficiently reduce the connection resistance between electrically connected circuit electrodes.

另外，上述实施方式中，作为粘接剂成分5，使用的是含有至少由加热而产生自由基的自由基聚合引发剂的物质，但也可以使用只用光照射就能产生自由基的自由基聚合引发剂来替代该自由基聚合引发剂。这时，在膜状电路连接材料40的固化处理时，用光照射代替加热即可。另外，上述实施方式中，使用膜状电路连接材料40来制造电路部件的连接结构，但也可以使用没有形成膜状的电路连接材料来代替膜状电路连接材料40。这时，只要将电路连接材料溶解在溶剂中，将其溶液涂布于第一电路部件20或第二电路部件30的任何一方并进行干燥，就可以使电路连接材料介于第一和第二电路部件20、30间。In addition, in the above-mentioned embodiment, as the adhesive agent component 5, a substance containing a radical polymerization initiator that generates radicals by at least heating is used, but a radical that generates radicals only by light irradiation may also be used. A polymerization initiator is used instead of the radical polymerization initiator. In this case, in the curing process of the film-form circuit connecting material 40 , it may be irradiated with light instead of heating. Moreover, in the said embodiment, the connection structure of a circuit component was manufactured using the film-form circuit connection material 40, However, You may use the circuit connection material which does not form a film form instead of the film-form circuit connection material 40. At this time, as long as the circuit connecting material is dissolved in a solvent, the solution is applied to either the first circuit member 20 or the second circuit member 30 and dried, the circuit connecting material can be interposed between the first and second circuit members. Between 20 and 30 circuit components.

另外，在电路部件连接结构的制造方法中，除了由加热或光照射来产生自由基的自由基聚合引发剂之外，还可以根据需要使用由超声波、电磁波等来产生自由基的自由基聚合引发剂。另外，作为粘接剂成分5，还可以使用环氧树脂和其潜在性固化剂。In addition, in the production method of the circuit component connection structure, in addition to the radical polymerization initiator that generates radicals by heating or light irradiation, a radical polymerization initiator that generates radicals by ultrasonic waves, electromagnetic waves, etc. may be used as needed. agent. In addition, as the adhesive component 5, epoxy resin and its latent curing agent can also be used.

另外，图4为显示使用本发明的膜状粘接剂而制造的半导体装置的一个实施方式的示意截面图。如图4所示，半导体装置2具有半导体元件50和作为半导体支撑部件的基板60，在半导体元件50和基板60之间设置电连接它们的半导体元件连接部件80。另外，半导体元件连接部件80层叠在基板60的主面60a上，半导体元件50进一步层叠在该半导体元件连接部件80上。In addition, FIG. 4 is a schematic cross-sectional view showing one embodiment of a semiconductor device manufactured using the film adhesive of the present invention. As shown in FIG. 4 , the semiconductor device 2 has a semiconductor element 50 and a substrate 60 serving as a semiconductor supporting member, and a semiconductor element connection member 80 electrically connecting them is provided between the semiconductor element 50 and the substrate 60 . In addition, a semiconductor element connection member 80 is laminated on the main surface 60 a of the substrate 60 , and the semiconductor element 50 is further laminated on the semiconductor element connection member 80 .

基板60具有电路图案61，电路图案61在基板60的主面60a上隔着半导体连接部件80或直接地与半导体元件50电连接。然后，由密封材70密封它们，形成半导体装置2。The substrate 60 has a circuit pattern 61 electrically connected to the semiconductor element 50 via the semiconductor connection member 80 or directly on the main surface 60 a of the substrate 60 . Then, these are sealed with a sealing material 70 to form the semiconductor device 2 .

作为半导体元件50的材料没有特别的限制，可以使用硅、锗的IVA族半导体元件，GaAs、InP、GaP、InGaAs、InGaAsP、AlGaAs、InAs、GaInP、AlInP、AlGaInP、GaNAs、GaNP、GaInNAs、GaInNP、GaSb、InSb、GaN、AlN、InGaN、InNAsP等IIIA-VA族化合物半导体元件，HgTe、HgCdTe、CdMnTe、CdS、CdSe、MgSe、MgS、ZnSe、ZeTe等IIA-VIA族化合物半导体元件，以及CuInSe(CIS)等各种各样的材料。The material of the semiconductor element 50 is not particularly limited, and a group IVA semiconductor element of silicon or germanium, GaAs, InP, GaP, InGaAs, InGaAsP, AlGaAs, InAs, GaInP, AlInP, AlGaInP, GaNAs, GaNP, GaInNAs, GaInNP, GaSb, InSb, GaN, AlN, InGaN, InNAsP and other IIIA-VA compound semiconductor components, HgTe, HgCdTe, CdMnTe, CdS, CdSe, MgSe, MgS, ZnSe, ZeTe and other IIA-VIA compound semiconductor components, and CuInSe (CIS ) and other various materials.

半导体元件连接部件80含有绝缘性物质11和导电性粒子7。导电性粒子7不仅配置在半导体元件50和电路图案61之间，还设置在半导体元件50和主面60a之间。在半导体装置2中，通过导电性粒子7电连接半导体元件50和电路图案61。因此，半导体元件50和电路图案61之间的连接电阻被充分降低。所以可以顺利地进行半导体元件50和电路图案61之间的电流流动，充分发挥半导体所具有的功能。The semiconductor element connection member 80 contains an insulating substance 11 and conductive particles 7 . The electroconductive particle 7 is arrange|positioned not only between the semiconductor element 50 and the circuit pattern 61, but also between the semiconductor element 50 and the main surface 60a. In the semiconductor device 2 , the semiconductor element 50 and the circuit pattern 61 are electrically connected via the conductive particles 7 . Therefore, connection resistance between the semiconductor element 50 and the circuit pattern 61 is sufficiently reduced. Therefore, the current flow between the semiconductor element 50 and the circuit pattern 61 can be smoothly performed, and the functions of the semiconductor can be fully exhibited.

另外，半导体元件连接部件80不含导电性粒子7时，按照希望的量的电流流过的方式使半导体元件50和电路图案61直接接触或充分接近，从而来进行电连接。In addition, when the semiconductor element connection member 80 does not contain the conductive particles 7, the semiconductor element 50 and the circuit pattern 61 are brought into direct contact or sufficiently close to each other so that a desired amount of current flows, and are electrically connected.

半导体元件连接部件80由上述本发明的膜状粘接剂的固化物而构成。所以，半导体元件连接部件80对半导体元件50和基板60的粘接强度非常高，且半导体元件50和电路图案61之间的连接电阻变得充分小。另外，半导体元件连接部件80是由低温短时间的加热处理被形成得到的部件。因此，半导体装置2可以具有比以往更高的可靠性。The semiconductor element connecting member 80 is composed of a cured product of the above-mentioned film adhesive of the present invention. Therefore, the adhesive strength of the semiconductor element connecting member 80 to the semiconductor element 50 and the substrate 60 is very high, and the connection resistance between the semiconductor element 50 and the circuit pattern 61 becomes sufficiently small. In addition, the semiconductor element connecting member 80 is formed by heat treatment at a low temperature and for a short time. Therefore, the semiconductor device 2 can have higher reliability than before.

另外，半导体装置2可以通过在上述的电路部件连接结构的制造方法中的第一和第二电路部件20、30中使用基板60和半导体元件50，以与上述电路部件的连接结构的制造方法相同的方法来制造。In addition, the semiconductor device 2 can be made the same as the manufacturing method of the above-mentioned circuit member connecting structure by using the substrate 60 and the semiconductor element 50 in the first and second circuit members 20, 30 in the manufacturing method of the above-mentioned circuit member connecting structure. method to manufacture.

实施例Example

以下，基于实施例和比较例对本发明具体说明，但本发明并未限于以下实施例。Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to a following example.

[苯氧树脂的准备][Preparation of phenoxy resin]

将40g的苯氧树脂(商品名：YP-50、东都化成社制)溶解于60g的甲基乙基酮中，形成固体成分为40质量％的溶液。40 g of phenoxy resin (trade name: YP-50, manufactured by Tohto Kasei Co., Ltd.) was dissolved in 60 g of methyl ethyl ketone to obtain a solution with a solid content of 40% by mass.

[聚酯型聚氨酯树脂的准备][Preparation of polyester polyurethane resin]

作为聚酯型聚氨酯树脂(商品名：UR-1400，东洋纺社制造)，使用的是固体成分为30质量％的甲基乙基酮和甲苯的1∶1(质量比)的混合溶剂溶解品。As the polyester polyurethane resin (trade name: UR-1400, manufactured by Toyobo Co., Ltd.), a 1:1 (mass ratio) mixed solvent solution of methyl ethyl ketone and toluene with a solid content of 30% by mass was used .

[自由基聚合性化合物的准备][Preparation of radically polymerizable compound]

准备异氰尿酸EO改性二丙烯酸酯(商品名：M-215，东亚合成株式会社制)。Isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toagosei Co., Ltd.) was prepared.

[氨酯丙烯酸酯的合成][Synthesis of urethane acrylate]

在安装有搅拌机、温度计、具有氯化钙干燥管的回流冷却管以及氮气导管的反应容器中，投入860g(1.00摩尔)的数均分子量为860的聚(六甲亚基碳酸酯)二醇(Aldrich社制)和5.53g的二月桂酸二丁基锡(Aldrich社制)。在反应容器中导入充分的氮气后，加热至70～75℃，用3小时均匀滴下666g(3.00摩尔)的异佛尔酮二异氰酸酯，使其反应。In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube with a calcium chloride drying tube, and a nitrogen conduit, 860 g (1.00 moles) of poly(hexamethylene carbonate) glycol (Aldrich Co., Ltd.) and 5.53 g of dibutyltin dilaurate (manufactured by Aldrich). After introducing sufficient nitrogen into the reaction vessel, it was heated to 70 to 75° C., and 666 g (3.00 mol) of isophorone diisocyanate was uniformly dropped and reacted over 3 hours.

滴下结束后，继续反应10小时。在其中投入238g(2.05摩尔)的丙烯酸2-羟基乙基酯(Aldrich社制)和0.53g的氢醌单甲基醚(Aldrich社制)，进一步反应10小时后，由IR测定确认异氰酸酯消失后，终止反应，得到氨酯丙烯酸酯(UA)。得到的UA的数均分子量为3,700。After completion of the dropping, the reaction was continued for 10 hours. 238 g (2.05 moles) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 g of hydroquinone monomethyl ether (manufactured by Aldrich) were put into it, and after further reacting for 10 hours, the disappearance of the isocyanate was confirmed by IR measurement , to terminate the reaction to obtain urethane acrylate (UA). The number average molecular weight of the obtained UA was 3,700.

[含有磷酸基的乙烯化合物的准备][Preparation of vinyl compound containing phosphoric acid group]

准备2-(甲基)丙烯酰氧基乙基磷酸酯(商品名：轻酯(ライトエステル)P-2M，共荣社株式会社制)。2-(Meth)acryloyloxyethyl phosphate (trade name: light ester (Light Ester) P-2M, manufactured by Kyoeisha Co., Ltd.) was prepared.

[苯氧树脂的准备][Preparation of phenoxy resin]

作为环氧树脂，准备PO改性BisA型环氧树脂(商品名：ADEKA RESINEP-4010S，株式会社ADEKA制)。As the epoxy resin, a PO-modified BisA type epoxy resin (trade name: ADEKA RESINEP-4010S, manufactured by ADEKA Corporation) was prepared.

[有机微粒的准备][Preparation of Organic Particles]

作为有机微粒，分别准备具有三维交联结构的甲基丙烯酸烷基酯-丁二烯-苯乙烯共聚物(商品名：Metablen C-223A，三菱丽阳社制，Tg：-70℃，平均粒径：400nm)和丙烯酸-有机硅共聚物(商品名：Shariene R-210，日信化学工业社制，Tg：-80℃，平均粒径：200nm)。As organic fine particles, an alkyl methacrylate-butadiene-styrene copolymer having a three-dimensional crosslinked structure (trade name: Metablen C-223A, manufactured by Mitsubishi Rayon Corporation, Tg: -70°C, average particle size Diameter: 400nm) and acrylic-silicone copolymer (trade name: Shariene R-210, manufactured by Nissin Chemical Industry Co., Ltd., Tg: -80°C, average particle diameter: 200nm).

[交联聚丁二烯粒子的准备][Preparation of cross-linked polybutadiene particles]

在不锈钢制的高压釜中放入纯水，然后在其中添加作为悬浮剂的聚乙烯醇(关东化学社制)并使其溶解。在其中加入丁二烯(Aldrich社制)，搅拌使其分散。进一步加入作为自由基聚合引发剂的过氧化苯甲酰(商品名：力ドツクスCH-50L，化药AKZO社制)，搅拌使其溶解。Pure water was placed in a stainless steel autoclave, and polyvinyl alcohol (manufactured by Kanto Chemical Co., Ltd.) was added and dissolved therein as a suspending agent. Butadiene (manufactured by Aldrich) was added thereto, stirred and dispersed. Further, benzoyl peroxide (trade name: Redoux CH-50L, manufactured by Kayaku AKZO Co., Ltd.) was added as a radical polymerization initiator, and stirred to dissolve it.

然后，将高压釜升温至60～65℃，一边搅拌一边聚合45分钟。然后，放出未反应的单体后，过滤生成的交联聚丁二烯粒子，用水清洗，用乙醇清洗。将洗净后的交联聚丁二烯粒子在真空中干燥，得到平均粒径为500nm的交联聚丁二烯粒子(BR)。Then, the temperature of the autoclave was raised to 60 to 65° C., and polymerization was carried out for 45 minutes while stirring. Then, after releasing unreacted monomers, the generated crosslinked polybutadiene particles were filtered, washed with water, and washed with ethanol. The washed crosslinked polybutadiene particles were dried in vacuum to obtain crosslinked polybutadiene particles (BR) with an average particle diameter of 500 nm.

[自由基聚合引发剂][Radical polymerization initiator]

作为自由基聚合引发剂，准备叔己基过氧化-2-乙基己酸酯(商品名：PERHEXYL O，日本油脂株式会社制)。As a radical polymerization initiator, tert-hexylperoxy-2-ethylhexanoate (trade name: PERHEXYLO, manufactured by NOF Corporation) was prepared.

[潜在性固化剂的准备][Preparation of latent curing agent]

作为潜在性固化剂，准备锍盐(商品名：サンエイドSI-60L，三新化成工业株式会社制)。As a latent curing agent, a sulfonium salt (trade name: SunEid SI-60L, manufactured by Sanshin Chemical Industry Co., Ltd.) was prepared.

[导电性粒子的制作][Production of conductive particles]

将厚度为0.2μm的由镍形成的层设置在聚苯乙烯粒子的表面上，然后，在由该镍形成的层的表面上进一步设置厚度为0.02μm的由金形成的层。这样制成平均粒径为4μm，比重为2.5的导电性粒子。A layer made of nickel with a thickness of 0.2 μm was provided on the surface of the polystyrene particles, and then a layer made of gold with a thickness of 0.02 μm was further provided on the surface of the layer made of nickel. Thus, the average particle diameter was 4 micrometers, and the electroconductive particle whose specific gravity was 2.5 was produced.

实施例1～10，比较例1～5Examples 1-10, Comparative Examples 1-5

以固体成分质量比为下述表1所示的比例(单位：质量份)混合上述的各材料，然后进一步混合分散上述导电性粒子使其成为得到的粘接剂组合物的固体成分总体积的1.5体积％，得到粘接剂组合物。使用涂布装置将得到的粘接剂组合物涂布在厚度为80μm的氟树脂膜上，在70℃进行10分钟的热风干燥，从而得到粘接剂层的厚度为20μm的膜状粘接剂。The above-mentioned materials were mixed with the solid content mass ratio as shown in the following Table 1 (unit: parts by mass), and then the above-mentioned conductive particles were further mixed and dispersed so that it became the total volume of the solid content of the adhesive composition obtained. 1.5% by volume to obtain an adhesive composition. Apply the obtained adhesive composition on a fluororesin film with a thickness of 80 μm using a coating device, and dry it with hot air at 70° C. for 10 minutes to obtain a film-shaped adhesive with an adhesive layer thickness of 20 μm .

[粘接强度和连接电阻的测定][Measurement of Adhesive Strength and Connection Resistance]

使用实施例和比较例中得到的膜状粘接剂，使用热压接装置(加热方式：恒热型、东丽工程株式会社制)，在温度160℃、压力3MPa的条件下，对具有500根线宽为25μm、间距为50μm和厚度为18μm铜电路的挠性线路板(FPC)以及形成有厚度为0.2μm氧化铟(ITO)薄层的玻璃(厚度为1.1mm、表面电阻为20Ω/□)进行10秒的加热加压。由此，制成由膜状粘接剂固化物以2mm的宽度连接FPC基板和ITO基板的连接体(电路部件的连接结构)。Using the film adhesives obtained in Examples and Comparative Examples, using a thermocompression bonding device (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), under the conditions of a temperature of 160 ° C and a pressure of 3 MPa, a pair with 500 A flexible circuit board (FPC) with a copper circuit with a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm, and glass formed with a thin layer of indium oxide (ITO) with a thickness of 0.2 μm (thickness 1.1 mm, surface resistance 20Ω/ □) Heat and pressurize for 10 seconds. In this way, a connected body (connection structure of circuit components) in which the FPC board and the ITO board were connected with a width of 2 mm by the film-shaped adhesive cured product was produced.

用万用表测定粘接后即刻以及在85℃、85％RH的高温高湿槽中保持250小时后的该连接体的连接电路间的电阻值(连接电阻)。以连接电路间的电阻37点的平均值表示电阻值。结果示于表2中。The resistance value (connection resistance) between the connected circuits of the connected body was measured with a multimeter immediately after bonding and after being kept in a high-temperature, high-humidity chamber at 85° C. and 85% RH for 250 hours. The resistance value is expressed as an average value of 37 points of resistance between connected circuits. The results are shown in Table 2.

根据JIS-Z0237以90度剥离法测定该连接体的粘接强度，进行评价。这里，粘接强度的测定装置使用的是东洋宝德温株式会社(東洋ボ一ルドウイン株式会社)制造的天斯隆(テンシロン)UTM-4(剥离速度为50mm/min，25℃)。结果示于表2中。The adhesive strength of this connected body was measured and evaluated by the 90 degree peeling method based on JIS-Z0237. Here, the measuring device of the adhesive strength used Tensiron UTM-4 (peeling speed: 50 mm/min, 25° C.) manufactured by Toyo Baldwin Co., Ltd. (Toyo Baldwin Co., Ltd.). The results are shown in Table 2.

表2Table 2

Figure G2008800242836D00231
Figure G2008800242836D00231

从表2所示的结果可知，实施例1～10所得到的膜状粘接剂，在加热温度160℃、时间10秒的连接条件下，在粘接后即刻以及在85℃、85％RH的高温高湿槽中保持250小时后这两种情况下都确认出显示良好的连接电阻和粘接强度，显示良好的特性。From the results shown in Table 2, it can be seen that the film adhesives obtained in Examples 1 to 10, under the connection conditions of a heating temperature of 160°C and a time of 10 seconds, immediately after bonding and at 85°C and 85%RH In both cases, after holding in the high-temperature, high-humidity tank for 250 hours, it was confirmed that good connection resistance and adhesive strength were exhibited, showing good characteristics.

与此相反，没有使用本发明的有机微粒的比较例1～2以及4～5中，发现在粘接后即刻以及在高温高湿处理后这两种情况下，粘接强度都差，高温高湿处理后粘接强度下降和连接电阻上升。另外，使用交联聚丁二烯粒子代替本发明的有机微粒的比较例3中，发现粘接后即刻和高温高湿处理后这两种情况下，连接强度都差，在高温高湿处理后粘接强度大幅度下降和连接电阻大幅度上升。In contrast, in Comparative Examples 1 to 2 and 4 to 5 in which the organic fine particles of the present invention were not used, it was found that both immediately after bonding and after high-temperature and high-humidity treatment, the bonding strength was poor, and the high temperature was high. The bond strength decreased and the connection resistance increased after wet treatment. In addition, in Comparative Example 3 in which cross-linked polybutadiene particles were used instead of the organic microparticles of the present invention, it was found that the connection strength was poor both immediately after bonding and after high-temperature and high-humidity treatment, and after high-temperature and high-humidity treatment. Adhesive strength decreased substantially and connection resistance increased substantially.

工业上的应用性Industrial applicability

如以上说明所述，根据本发明，可以提供一种显示优异的粘接强度，即使在可靠性试验(例如，85℃/85％RH放置)后也可以维持稳定性能的粘接剂组合物、使用该粘接剂组合物的膜状粘接剂和电路部件的连接结构。As described above, according to the present invention, it is possible to provide an adhesive composition that exhibits excellent adhesive strength and maintains stable performance even after a reliability test (for example, standing at 85°C/85%RH), A connection structure between a film adhesive and a circuit component using the adhesive composition.

Claims (14)

1.一种粘接剂组合物，其特征在于，含有(a)包含从(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚物或复合物、(甲基)丙烯酸烷基酯-有机硅共聚物或复合物和有机硅-(甲基)丙烯酸共聚物或复合物组成的组中选出的至少一种物质的有机微粒。1. An adhesive composition, is characterized in that, contains (a) comprises from (meth) alkyl acrylate-butadiene-styrene copolymer or compound, (meth) acrylate- Organic fine particles of at least one substance selected from the group consisting of silicone copolymers or composites and silicone-(meth)acrylic copolymers or composites. 2.根据权利要求1所述的粘接剂组合物，其中，含有(b)自由基聚合性化合物和(c)自由基聚合引发剂。2. The adhesive composition according to claim 1, comprising (b) a radical polymerizable compound and (c) a radical polymerization initiator. 3.根据权利要求1所述的粘接剂组合物，其中，含有(d)环氧树脂和(e)潜在性固化剂。3. The adhesive composition according to claim 1, comprising (d) an epoxy resin and (e) a latent curing agent. 4.根据权利要求1～3中任一项所述的粘接剂组合物，其中，所述(a)有机微粒的Tg为-100～70℃。4. The adhesive composition according to any one of claims 1 to 3, wherein the (a) organic fine particles have a Tg of -100 to 70°C. 5.根据权利要求1～4中任一项所述的粘接剂组合物，其中，所述(a)有机微粒为包含具有三维交联结构的聚合物的粒子。5. The adhesive composition according to any one of claims 1 to 4, wherein the (a) organic fine particles are particles containing a polymer having a three-dimensional crosslinked structure. 6.根据权利要求1～5中任一项所述的粘接剂组合物，其中，所述(a)有机微粒为包含重均分子量为100万～300万的聚合物的粒子。6 . The adhesive composition according to claim 1 , wherein the (a) organic fine particles are particles containing a polymer having a weight average molecular weight of 1 million to 3 million. 7.根据权利要求1～6中任一项所述的粘接剂组合物，其中，以粘接剂组合物的固体成分总量为基准，所述(a)有机微粒的含量为5～80质量％。7. The adhesive composition according to any one of claims 1 to 6, wherein, based on the total solid content of the adhesive composition, the content of (a) organic microparticles is 5 to 80 quality%. 8.根据权利要求1～7中任一项所述的粘接剂组合物，其中，所述(a)有机微粒为具有核壳结构的粒子。8. The adhesive composition according to any one of claims 1 to 7, wherein the (a) organic fine particles are particles having a core-shell structure. 9.根据权利要求1～8中任一项所述的粘接剂组合物，其中，含有(f)分子内具有一个以上磷酸基的乙烯系化合物。9. The adhesive composition according to any one of claims 1 to 8, which contains (f) a vinyl compound having one or more phosphoric acid groups in the molecule. 10.根据权利要求1～9中任一项所述的粘接剂组合物，其中，含有(g)热塑性树脂。10. The adhesive composition according to any one of claims 1 to 9, which contains (g) a thermoplastic resin. 11.根据权利要求10所述的粘接剂组合物，其中，所述(g)热塑性树脂含有从苯氧树脂、聚酯树脂、聚氨酯树脂、聚酯型聚氨酯树脂、丁醛树脂、丙烯酸树脂和聚酰亚胺树脂组成的组中选出的至少一种。11. The adhesive composition according to claim 10, wherein, the (g) thermoplastic resin contains phenoxy resin, polyester resin, polyurethane resin, polyester polyurethane resin, butyral resin, acrylic resin and At least one selected from the group consisting of polyimide resins. 12.根据权利要求1～11中任一项所述的粘接剂组合物，其中，含有(h)导电性粒子。The adhesive composition in any one of Claims 1-11 containing (h) electroconductive particle. 13.一种膜状粘接剂，是将权利要求1～12中任一项所述的粘接剂组合物形成为膜状而成的。13. A film-shaped adhesive obtained by forming the adhesive composition according to any one of claims 1 to 12 into a film. 14.一种电路部件的连接结构，其具备：14. A connection structure of circuit components, comprising: 相对设置的一对电路部件；以及a pair of circuit components disposed opposite; and 设置在所述一对电路部件之间的连接部件，该连接部件按照使所述一对电路部件所具有的电路电极彼此被电连接的方式将电路部件彼此粘接；a connection member provided between the pair of circuit components, the connection member bonding the circuit components to each other in such a manner that circuit electrodes of the pair of circuit components are electrically connected to each other; 其中，所述连接部件是由权利要求1～12中任一项所述的粘接剂组合物的固化物形成的部件。Here, the connecting member is a member formed of a cured product of the adhesive composition according to any one of claims 1 to 12.
CN200880024283.6A 2007-08-08 2008-07-29 Adhesive composition, film adhesive, and connection structure of circuit components Active CN101688099B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201210004210.9A CN102585709B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block
CN201210004719.3A CN102559072B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP206871/2007 2007-08-08
JP2007206871 2007-08-08
PCT/JP2008/063543 WO2009020005A1 (en) 2007-08-08 2008-07-29 Adhesive composition, film-like adhesive, and connection structure for circuit member

Related Child Applications (4)

Application Number Title Priority Date Filing Date
CN201210004210.9A Division CN102585709B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block
CN201210004719.3A Division CN102559072B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block
CN2012100041731A Division CN102559071A (en) 2007-08-08 2008-07-29 Adhesive composition, film-like adhesive, and connection structure for circuit member
CN201410528209.5A Division CN104263291A (en) 2007-08-08 2008-07-29 Adhesive Composition, Film-like Adhesive, And Connection Structure For Circuit Member

Publications (2)

Publication Number Publication Date
CN101688099A true CN101688099A (en) 2010-03-31
CN101688099B CN101688099B (en) 2016-08-03

Family

ID=40341240

Family Applications (5)

Application Number Title Priority Date Filing Date
CN201410528209.5A Pending CN104263291A (en) 2007-08-08 2008-07-29 Adhesive Composition, Film-like Adhesive, And Connection Structure For Circuit Member
CN201210004210.9A Expired - Fee Related CN102585709B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block
CN2012100041731A Pending CN102559071A (en) 2007-08-08 2008-07-29 Adhesive composition, film-like adhesive, and connection structure for circuit member
CN200880024283.6A Active CN101688099B (en) 2007-08-08 2008-07-29 Adhesive composition, film adhesive, and connection structure of circuit components
CN201210004719.3A Active CN102559072B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block

Family Applications Before (3)

Application Number Title Priority Date Filing Date
CN201410528209.5A Pending CN104263291A (en) 2007-08-08 2008-07-29 Adhesive Composition, Film-like Adhesive, And Connection Structure For Circuit Member
CN201210004210.9A Expired - Fee Related CN102585709B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block
CN2012100041731A Pending CN102559071A (en) 2007-08-08 2008-07-29 Adhesive composition, film-like adhesive, and connection structure for circuit member

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201210004719.3A Active CN102559072B (en) 2007-08-08 2008-07-29 The syndeton of adhesive composite, film-like adhesive and circuit block

Country Status (7)

Country Link
US (1) US20120048606A1 (en)
EP (1) EP2180026A4 (en)
JP (2) JP5012903B2 (en)
KR (4) KR20100049639A (en)
CN (5) CN104263291A (en)
TW (2) TWI525166B (en)
WO (1) WO2009020005A1 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295892A (en) * 2010-06-14 2011-12-28 日立化成工业株式会社 Circuit connecting adhesive film and use thereof, structure body, manufacturing method and connection method thereof
CN102295894A (en) * 2010-06-14 2011-12-28 日立化成工业株式会社 Circuit connecting adhesive film and use thereof, structure body, manufacturing method and connection method thereof
CN102382581A (en) * 2010-06-14 2012-03-21 日立化成工业株式会社 An adhesive film for circuit connection, use thereof, a circuit connection structure, a manufacturing method thereof, and a connection method of a circuit member
CN102382580A (en) * 2010-06-14 2012-03-21 日立化成工业株式会社 An adhesive film for circuit connection, use thereof, a circuit connection structure, a manufacturing method thereof, and a connection method of a circuit member
CN103087650A (en) * 2011-11-04 2013-05-08 第一毛织株式会社 Composition for anisotropic conductive adhesive film, anisotropic conductive adhesive film and semiconductor device
CN103160217A (en) * 2011-12-16 2013-06-19 第一毛织株式会社 Anisotropic conductive film composition, the anisotropic conductive film thereof and semiconductor device
CN103173144A (en) * 2011-12-26 2013-06-26 第一毛织株式会社 Composition for anisotropic conductive adhesive film, anisotropic conductive adhesive film and semiconductor device
CN103596363A (en) * 2013-10-26 2014-02-19 溧阳市东大技术转移中心有限公司 Composite flexible substrate
CN103865411A (en) * 2012-12-12 2014-06-18 第一毛织株式会社 Adhesive film for polarizing plate, adhesive composition for the same, polarizing plate comprising the same, and optical display apparatus comprising the same
CN104137240A (en) * 2012-02-24 2014-11-05 日立化成株式会社 Adhesive for semiconductor, flux, manufacturing method of semiconductor device, and semiconductor device
CN104342080A (en) * 2013-07-26 2015-02-11 日立化成株式会社 Adhesive composition, circuit connecting material, circuit connection structure, and adhesive sheet
US9425120B2 (en) 2012-02-24 2016-08-23 Hitachi Chemical Company, Ltd Semiconductor device and production method therefor
WO2020042247A1 (en) * 2018-08-31 2020-03-05 深圳市华星光电技术有限公司 Silicon-based spherical particle, sealant, and liquid crystal display screen
CN114410255A (en) * 2022-01-14 2022-04-29 安徽富印新材料有限公司 High-cohesion pressure-sensitive adhesive and preparation method thereof
CN116472320A (en) * 2020-11-24 2023-07-21 株式会社力森诺科 Adhesive film for circuit connection, circuit connection structure, and method for manufacturing same

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5560544B2 (en) * 2007-08-29 2014-07-30 日立化成株式会社 Adhesive composition, film adhesive, circuit connecting adhesive, connector, and semiconductor device
JP2010225312A (en) * 2009-03-19 2010-10-07 Hitachi Chem Co Ltd Resin paste composition and semiconductor device
JP5569121B2 (en) * 2009-05-29 2014-08-13 日立化成株式会社 Adhesive composition, circuit member connecting adhesive sheet, and method for manufacturing semiconductor device
JP5569126B2 (en) * 2009-05-29 2014-08-13 日立化成株式会社 Adhesive composition, adhesive sheet, and method for manufacturing semiconductor device
KR101184910B1 (en) 2009-11-02 2012-09-20 회명산업 주식회사 Anisotropic conductive adhesive having superior repairability and fast adhesiveness
BR112012011798B1 (en) * 2009-11-17 2020-12-08 Hitachi Chemical Company, Ltd. circuit connection material, connection structure using the same and temporary pressure connection method
JP2011204898A (en) * 2010-03-25 2011-10-13 Hitachi Chem Co Ltd Adhesive composition, and connection structure for circuit member
JP5206840B2 (en) * 2010-06-14 2013-06-12 日立化成株式会社 Adhesive film for circuit connection, circuit connection structure using the same, and circuit member connection method
KR101279980B1 (en) 2010-12-29 2013-07-05 제일모직주식회사 Anisotropic conductive film composition and the anisotropic conductive film thereof
US9281097B2 (en) 2010-12-29 2016-03-08 Cheil Industries, Inc. Anisotropic conductive film, composition for the same, and apparatus including the same
WO2013042203A1 (en) 2011-09-20 2013-03-28 日立化成株式会社 Adhesive composition, film adhesive, adhesive sheet, circuit connector and circuit member connection method
KR101403865B1 (en) * 2011-12-16 2014-06-10 제일모직주식회사 Composition for use in an anisotropic conductive film, an anisotropic conductive film and semiconductor device
GB2504957A (en) * 2012-08-14 2014-02-19 Henkel Ag & Co Kgaa Curable compositions comprising composite particles
JP6107175B2 (en) * 2013-01-29 2017-04-05 日立化成株式会社 Circuit connection material, circuit member connection structure, and method of manufacturing circuit member connection structure
TWI591151B (en) 2013-05-24 2017-07-11 明基材料股份有限公司 Adhesive composition for conduction between electrical elements
CN103596355A (en) * 2013-10-26 2014-02-19 溧阳市东大技术转移中心有限公司 Double-layer flexible printed circuit board
WO2015068611A1 (en) * 2013-11-07 2015-05-14 東洋インキＳｃホールディングス株式会社 Electroconductive adhesive, electroconductive adhesive sheet, wiring device, and method for manufacturing wiring device
US9558787B2 (en) 2014-01-29 2017-01-31 Google Inc. Media application backgrounding
CN105493207B (en) * 2014-02-24 2018-05-25 积水化学工业株式会社 Method for manufacturing a connected structure
JP2015168803A (en) 2014-03-10 2015-09-28 日立化成株式会社 Conductive adhesive composition, connector, solar cell module and method for producing the same
JP6374192B2 (en) * 2014-03-25 2018-08-15 デクセリアルズ株式会社 Anisotropic conductive film, connection method, and joined body
KR102411356B1 (en) * 2014-09-18 2022-06-22 세키스이가가쿠 고교가부시키가이샤 Electrically conductive paste, joined structure, and method for manufacturing joined structure
CN104388003A (en) * 2014-11-25 2015-03-04 常熟市长江胶带有限公司 High-strength belt-shaped conductive foam adhesive
JP6285346B2 (en) 2014-12-08 2018-02-28 信越化学工業株式会社 Transparent resin composition, adhesive comprising the composition, die-bonding material comprising the composition, conductive connection method using the composition, and optical semiconductor device obtained by the method
KR101822700B1 (en) * 2014-12-23 2018-01-30 삼성에스디아이 주식회사 Adhesive composition, adhesive film prepared by the same and display member comprising the same
JP6757558B2 (en) * 2015-07-09 2020-09-23 信越ポリマー株式会社 Thermoplastic polyurethane elastomer composition, flexible material, and communication cable
JP6710120B2 (en) * 2015-09-30 2020-06-17 太陽インキ製造株式会社 Conductive adhesive, electronic component, and method for manufacturing electronic component
CN106832103B (en) * 2017-01-05 2019-02-19 无锡海特新材料研究院有限公司 A kind of acrylate pressure-sensitive adhesive and preparation method thereof of strong adherence PC substrate
US11135551B2 (en) * 2017-03-20 2021-10-05 Bl Technologies, Inc. Ion-exchange membrane having an imprinted non-woven substrate
KR102837107B1 (en) * 2017-03-29 2025-07-22 가부시끼가이샤 레조낙 Adhesive compositions and structures
JP7046351B2 (en) 2018-01-31 2022-04-04 三国電子有限会社 How to make a connection structure
JP7160302B2 (en) 2018-01-31 2022-10-25 三国電子有限会社 CONNECTED STRUCTURE AND METHOD OF MAKING CONNECTED STRUCTURE
JP7185252B2 (en) 2018-01-31 2022-12-07 三国電子有限会社 Method for producing connection structure
TWI789506B (en) * 2018-03-27 2023-01-11 日商迪愛生股份有限公司 Curable adhesive composition, adhesive sheet using the composition, laminate containing the adhesive sheet, and manufacturing method thereof
JP2018178125A (en) * 2018-06-26 2018-11-15 日立化成株式会社 Conductive adhesive composition, connection body, solar cell module and method for producing the same
CN110387193A (en) * 2019-08-09 2019-10-29 苏州凡赛特材料科技有限公司 A kind of nano metal conductive film optics Adhesive composition and its glue film
CN110964462B (en) * 2019-12-09 2021-06-29 南京金世家新材料科技有限公司 Single-component conductive adhesive stored and cured at normal temperature and preparation method and application thereof
CN111239323A (en) * 2020-02-13 2020-06-05 湖南瀚洋环保科技有限公司 Rapid detection method for hazardous waste hazard characteristics
CN111334198B (en) * 2020-03-27 2021-10-15 顺德职业技术学院 UV two-component dual-curing structural adhesive
GB2593754B (en) * 2020-04-01 2022-12-28 Henkel Ag & Co Kgaa Redox curable compositions and methods of manufacture thereof

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808180A (en) * 1970-04-13 1974-04-30 Rohm & Haas Composite interpolymer and low haze impact resistant thermoplastic compositions thereof
US4759983A (en) * 1986-05-30 1988-07-26 Union Oil Company Of California Pressure sensitive adhesives and adhesive articles
JP2610900B2 (en) 1987-10-27 1997-05-14 ソニーケミカル 株式会社 Thermosetting anisotropic conductive adhesive sheet and method for producing the same
CA2015905A1 (en) * 1989-05-16 1990-11-16 Louis Christopher Graziano Acrylic adhesive compositions containing crosslinking agents and impact modifiers
US5371327A (en) * 1992-02-19 1994-12-06 Shin-Etsu Polymer Co., Ltd. Heat-sealable connector sheet
US5360861A (en) * 1993-05-28 1994-11-01 General Electric Company Polyester-carbonate resin compositions of improved impact-resistance
JP2627051B2 (en) * 1994-03-30 1997-07-02 大日本塗料株式会社 Water-based thermal adhesion type coating composition
JP3137578B2 (en) * 1996-02-27 2001-02-26 ソニーケミカル株式会社 Conductive particles for anisotropic conductive adhesive film, method for producing the same, and anisotropic conductive adhesive film
JPH10147685A (en) * 1996-11-18 1998-06-02 Toagosei Co Ltd Resin composition for insulation material
JP3477367B2 (en) 1998-05-12 2003-12-10 ソニーケミカル株式会社 Anisotropic conductive adhesive film
JP2000109783A (en) * 1998-10-01 2000-04-18 Denki Kagaku Kogyo Kk Adhesive composition, metal panel, and method for bonding metal sheet and reinforcing plate
JP3491595B2 (en) * 2000-02-25 2004-01-26 ソニーケミカル株式会社 Anisotropic conductive adhesive film
JP3522634B2 (en) 2000-03-21 2004-04-26 住友ベークライト株式会社 Anisotropic conductive adhesive
JP4590732B2 (en) 2000-12-28 2010-12-01 日立化成工業株式会社 Circuit connection material, circuit board manufacturing method using the same, and circuit board
JP2002285128A (en) 2001-03-26 2002-10-03 Sumitomo Bakelite Co Ltd Adhesive having anisotropic electric conductivity
JP2002285103A (en) 2001-03-26 2002-10-03 Sumitomo Bakelite Co Ltd Anisotropic electroconductive adhesive
JP2002285135A (en) * 2001-03-27 2002-10-03 Shin Etsu Polymer Co Ltd Anisotropic electroconductive adhesive and connecting structure using the same
JP2003049151A (en) * 2001-08-02 2003-02-21 Hitachi Chem Co Ltd Adhesive for connecting circuit, connecting method using the same and connecting structure
JP3864078B2 (en) * 2001-11-30 2006-12-27 三井化学株式会社 Anisotropic conductive paste and method of using the same
US6949602B2 (en) * 2002-12-19 2005-09-27 Illinois Tool Works, Inc. Heat resistant, impact resistant, acrylic/epoxy adhesives
JP4160512B2 (en) * 2004-01-20 2008-10-01 株式会社リコー Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and process cartridge for image forming apparatus
JP4767523B2 (en) 2004-07-05 2011-09-07 株式会社リコー Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and process cartridge for image forming apparatus
KR100638434B1 (en) * 2004-10-25 2006-10-24 주식회사 엘지화학 Silicone-acrylic impact modifier having excellent colorability and thermoplastic resin composition comprising the same
EP1860170A4 (en) * 2005-03-16 2010-05-05 Hitachi Chemical Co Ltd Adhesive composition, circuit connecting material, connection structure of circuit member, and semiconductor device
JP2008195852A (en) * 2007-02-14 2008-08-28 Hitachi Chem Co Ltd Film adhesive composition and joined structure in circuit terminal using the same composition

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295894B (en) * 2010-06-14 2014-12-31 日立化成株式会社 Circuit connecting adhesive film and use thereof, structure body, manufacturing method and connection method thereof
CN102295894A (en) * 2010-06-14 2011-12-28 日立化成工业株式会社 Circuit connecting adhesive film and use thereof, structure body, manufacturing method and connection method thereof
CN102382581A (en) * 2010-06-14 2012-03-21 日立化成工业株式会社 An adhesive film for circuit connection, use thereof, a circuit connection structure, a manufacturing method thereof, and a connection method of a circuit member
CN102382580A (en) * 2010-06-14 2012-03-21 日立化成工业株式会社 An adhesive film for circuit connection, use thereof, a circuit connection structure, a manufacturing method thereof, and a connection method of a circuit member
CN102295892A (en) * 2010-06-14 2011-12-28 日立化成工业株式会社 Circuit connecting adhesive film and use thereof, structure body, manufacturing method and connection method thereof
CN103087650A (en) * 2011-11-04 2013-05-08 第一毛织株式会社 Composition for anisotropic conductive adhesive film, anisotropic conductive adhesive film and semiconductor device
CN103087650B (en) * 2011-11-04 2016-03-16 第一毛织株式会社 For the composition of anisotropic conductive adhesive film, anisotropic conductive adhesive film and semiconductor device
CN103160217A (en) * 2011-12-16 2013-06-19 第一毛织株式会社 Anisotropic conductive film composition, the anisotropic conductive film thereof and semiconductor device
CN103173144B (en) * 2011-12-26 2015-05-20 第一毛织株式会社 Composition for anisotropic conductive adhesive film, anisotropic conductive adhesive film and semiconductor device
CN103173144A (en) * 2011-12-26 2013-06-26 第一毛织株式会社 Composition for anisotropic conductive adhesive film, anisotropic conductive adhesive film and semiconductor device
US9803111B2 (en) 2012-02-24 2017-10-31 Hitachi Chemical Company, Ltd. Adhesive for semiconductor, fluxing agent, manufacturing method for semiconductor device, and semiconductor device
CN104137240A (en) * 2012-02-24 2014-11-05 日立化成株式会社 Adhesive for semiconductor, flux, manufacturing method of semiconductor device, and semiconductor device
CN110556344A (en) * 2012-02-24 2019-12-10 日立化成株式会社 Adhesive for semiconductor, method for manufacturing semiconductor device, and semiconductor device
US9425120B2 (en) 2012-02-24 2016-08-23 Hitachi Chemical Company, Ltd Semiconductor device and production method therefor
CN103865411A (en) * 2012-12-12 2014-06-18 第一毛织株式会社 Adhesive film for polarizing plate, adhesive composition for the same, polarizing plate comprising the same, and optical display apparatus comprising the same
CN103865411B (en) * 2012-12-12 2017-01-11 第一毛织株式会社 Adhesive film for polarizing plate, adhesive composition for the same, polarizing plate comprising the same, and optical display apparatus comprising the same
CN104342080A (en) * 2013-07-26 2015-02-11 日立化成株式会社 Adhesive composition, circuit connecting material, circuit connection structure, and adhesive sheet
CN104342080B (en) * 2013-07-26 2019-03-08 日立化成株式会社 Adhesive composition, circuit connection material, circuit connection structure, and adhesive sheet
CN103596363A (en) * 2013-10-26 2014-02-19 溧阳市东大技术转移中心有限公司 Composite flexible substrate
WO2020042247A1 (en) * 2018-08-31 2020-03-05 深圳市华星光电技术有限公司 Silicon-based spherical particle, sealant, and liquid crystal display screen
CN116472320A (en) * 2020-11-24 2023-07-21 株式会社力森诺科 Adhesive film for circuit connection, circuit connection structure, and method for manufacturing same
CN114410255A (en) * 2022-01-14 2022-04-29 安徽富印新材料有限公司 High-cohesion pressure-sensitive adhesive and preparation method thereof

Also Published As

Publication number Publication date
KR101385899B1 (en) 2014-04-15
KR20120013440A (en) 2012-02-14
KR20120085319A (en) 2012-07-31
KR20120013441A (en) 2012-02-14
JP5012903B2 (en) 2012-08-29
CN102585709B (en) 2016-04-27
JP5454613B2 (en) 2014-03-26
CN101688099B (en) 2016-08-03
KR20100049639A (en) 2010-05-12
JPWO2009020005A1 (en) 2010-10-28
US20120048606A1 (en) 2012-03-01
WO2009020005A1 (en) 2009-02-12
EP2180026A4 (en) 2012-05-30
TWI525166B (en) 2016-03-11
CN102559072B (en) 2016-04-20
CN102559072A (en) 2012-07-11
CN104263291A (en) 2015-01-07
TW201315787A (en) 2013-04-16
CN102585709A (en) 2012-07-18
TW200932855A (en) 2009-08-01
EP2180026A1 (en) 2010-04-28
KR101552759B1 (en) 2015-09-11
KR101385391B1 (en) 2014-04-14
CN102559071A (en) 2012-07-11
TWI391458B (en) 2013-04-01
JP2012149274A (en) 2012-08-09

Similar Documents

Publication Publication Date Title
CN101688099B (en) Adhesive composition, film adhesive, and connection structure of circuit components
KR101025128B1 (en) Connection structure of adhesive composition and circuit member
CN104169389B (en) Circuit connection material, circuit connection structure, adhesive film and coiling body
JP4466650B2 (en) Film adhesive, film circuit connecting material, circuit member connecting method, and semiconductor device
CN102791820B (en) Adhesive composition and its use, and circuit component connection structure and its manufacturing method
JP2008195852A (en) Film adhesive composition and joined structure in circuit terminal using the same composition
JP5293779B2 (en) Adhesive composition, circuit connection structure, semiconductor device and solar cell module
JP5292838B2 (en) Adhesive and circuit member connection structure
JP5023901B2 (en) Adhesive composition, circuit connection structure, and semiconductor device
CN104559898A (en) Adhesive compositions and linkers
JP2011037953A (en) Adhesive agent composition, circuit-connecting structure and semiconductor device
JP2009074066A (en) Adhesive composition, film-shaped adhesive, adhesive for connecting circuits, connected body, and semiconductor device
JP5070748B2 (en) Adhesive composition, circuit connection material, connection body and semiconductor device
JP5338051B2 (en) Adhesive composition, circuit connection structure, and semiconductor device
JP2012204059A (en) Circuit connection material and circuit connection structure using the same
KR100973398B1 (en) Adhesive Compositions, Circuit Connection Structures, and Semiconductor Devices
JP2025043533A (en) Adhesive composition, adhesive film, laminate, and method for producing circuit connection structure

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: Japan Tokyo Chiyoda Marunouchi yidingmu 9 No. 2

Applicant after: HITACHI CHEMICAL Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: HITACHI CHEMICAL Co.,Ltd.

COR Change of bibliographic data
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: Japan Tokyo Chiyoda Marunouchi yidingmu 9 No. 2

Patentee after: Lishennoco Co.,Ltd.

Address before: Japan Tokyo Chiyoda Marunouchi yidingmu 9 No. 2

Patentee before: HITACHI CHEMICAL Co.,Ltd.